KR102204255B1 - Manufacturing method of superhydrophobic 6000 aluminum alloy for engines and automobile wheels - Google Patents

Abstract

The present invention relates to a method for manufacturing a 6000 series aluminum alloy anodized thin film having a super-hydrophobic surface and 6000 series aluminum alloy having an anodized thin film with a super-hydrophobic surface manufactured by using the same, in which an anodized aluminum layer formed on an aluminum alloy surface is implemented in a pillar-on-pore shape by adjusting anodizing voltage and time and pore expansion time, thereby providing an economic effect that the aluminum alloy with a controlled three-dimensional-shaped anodized thin film structure can be manufactured in a short time at low costs, and being available in various industrial fields such as an exterior case for a sensor, a cutting blade of a cutting mechanism, a housing of an electronic device, a cover of a lighting system like an LED, a heat exchanger, a pipe, a road structure, a car, an airplane, a ship, a power generator, etc. since the aluminum alloy manufactured by the same method has excellent super-hydrophobicity, corrosion resistance, durability, wear resistance and heat conductivity.

Description

Manufacturing method of superhydrophobic 6000 aluminum alloy for engines and automobile wheels}

The present invention relates to a method for manufacturing a superhydrophobic 6000 series aluminum alloy for an engine and automobile wheel, and a method for manufacturing a 6000 series aluminum alloy anodizing film having a superhydrophobic surface, and a 6000 having an anodized film having a superhydrophobic surface manufactured using the same. It relates to a series of aluminum alloys.

The aluminum oxide film with nano-sized pores arranged in a regular hexagonal structure was first studied and reported in 1995, and has been used in nanotechnology such as carbon nanotubes and nanowires using an aluminum anodizing process with an expanded range of applications. In addition, various nanotechnology researches are actively underway.

The pore diameter (D _P ) of the aluminum anodized film and the interpore distance (D _int ) are important factors in nanotechnology such as photovoltaic devices such as solar cells and LEDs and metal nanowires. It has a direct impact on performance in related applications and devices.

The electrochemical anodizing process has been used for surface treatment of metallic materials for over 70 years. Nanostructures fabricated through the anodization process can implement nanostructures with less cost and time compared to expensive electronic lithography or semiconductor etching processes using silicon. However, in the case of this anodized film, it has a two-dimensional porous arrangement that can control only the side dimensions. In addition, in the production of regularly arranged anodized aluminum films by controlling the type and concentration of the acid electrolyte of aluminum alloy, many studies and technologies such as the aquatic acid method, the sulfuric acid method, and the phosphoric acid method have been developed, but the type and concentration of the acid electrolyte change. The anodic oxidation process is limited in the increase of the pore diameter and the gap between the pores and the pores, and this technique is also possible only to produce a two-dimensional porous anodized film.

On the other hand, the pillar-on-pore (POP) structure, which is a structure in which a sharp pillar on top of the pore is formed in a single or bundle shape, is higher than that of the existing planar hexagonal porous surface. It has a contact angle and a low contact angle hysteresis, and thus has excellent superhydrophobic properties. In addition, the pillar-on-pore structure has properties such as hydrodynamic drag reduction, anticorrosion, anti-biofouling, and anti-icing, so it can realize the surface of smartphones and home appliances. It can play a big role.

However, a technique for forming such a pillar-on-pore structure on a semiconductor or high-purity aluminum substrate has been studied, but it is very difficult to form it on an alloy, and has not been studied yet. In general, a lot of research has been done on the technology for manufacturing a structure having a three-dimensional porous arrangement from an aluminum substrate of high purity, but in the actual industry, it is used in an alloy form rather than a high purity aluminum substrate, and it is intended for high purity aluminum substrates. When the researched technology is applied to an aluminum alloy used for actual commercialization, there is a problem that it is difficult to reproduce the same formation control.

In addition, forming a pillar-on-pore structure on the surface of a metal material is a technology of high difficulty, and an important factor for forming pillar-on-pores is anodization voltage/time/type of solvent (alone, mixed, etc.) /Solvent concentration, pore expansion treatment (PW) time/solvent type (chromic acid/phosphoric acid mixing ratio), etc.In order to form a pillar-on-pore structure, hard work is required to find a combination of effective treatment conditions from the above factors. It's a necessary skill.

In this regard, the applicants of the present invention have derived anodizing conditions for forming a pillar-on-pore structure on the surface of a 5000 series aluminum alloy through prior research. However, when the above conditions were applied to 6000 series aluminum alloys to produce an anodized film, the pillar-on-pore shape was not implemented, and the treatment conditions for forming the pillar-on-pore structure were different depending on the alloy type. Confirmed.

Accordingly, the applicant of the present invention adjusts the anodic oxidation voltage on the pre-patterned aluminum alloy in order to solve the conventional problems as described above and develop a method for forming a pillar-on-pore structure on a 6000 series aluminum alloy. Thus, by performing the second and third anodic oxidation processes and adjusting the pore expansion time, a three-dimensional porous film having various structures such as pillar-on-pores was produced to complete the present invention.

Korean Patent Registration No. 10-0935964

It is an object of the present invention to provide a method for producing a 6000 series aluminum alloy anodized film having a superhydrophobic surface.

Another object of the present invention is to provide a 6000 series aluminum alloy having an anodized film having a superhydrophobic surface manufactured by the above method.

Another object of the present invention is to provide a method for manufacturing a 6000 series aluminum alloy anodized film having a superhydrophobic surface having a bundled pillar-on-pore structure.

Another object of the present invention is to provide a 6000 series aluminum alloy with an anodized film having a superhydrophobic surface having a bundled pillar-on-pore structure manufactured by the above method.

To achieve the above object,

The present invention is a pre-patterning step of removing the primary anodization film by etching after the first anodization treatment of 6000 series aluminum alloy at 30-50V for 5-15 hours (step 1) ; Secondary anodizing the aluminum alloy for which pre-patterning has been completed in step 1 (step 2); Pore widening the aluminum alloy subjected to the secondary anodization treatment in step 2 (step 3); Tertiary anodizing the aluminum alloy for which pore expansion is completed in step 3 (step 4); And coating the aluminum alloy subjected to the third anodization in step 4 with a hydrophobic coating material (step 5), wherein the secondary anodization of step 2 is anodized at 30-50V for 15-45 minutes. It is characterized in that the anodization treatment is performed using a mild anodizing condition, and the pore expansion of step 3 is performed by adding 0.01-10M phosphoric acid (H ₃ PO) to the aluminum alloy that has undergone the secondary anodization treatment of step 2. ₄ ) It is characterized in that it is immersed in the solution for 25-47 minutes, and the third anodization of step 4 is a soft anodizing condition of anodizing at 30-50V for 15-45 minutes; And hard anodizing conditions for anodizing at 70-90V for 15-45 seconds. It provides a method for producing a 6000 series aluminum alloy anodizing film having a superhydrophobic surface, characterized in that the anodization treatment is performed using any one of conditions.

In addition, the present invention provides a 6000 series aluminum alloy having an anodized film having a superhydrophobic surface manufactured by the above method.

Further, the present invention is a pre-patterning step of removing the first anodized film by etching after the first anodization treatment of an aluminum alloy at 30-50V for 5-15 hours (step 1) ; In step 1, a pre-patterning step of removing the first anodized film by etching after first anodizing the 6000 series aluminum alloy at 30-50V for 5-15 hours (step 1 ); Secondary anodizing the aluminum alloy for which pre-patterning has been completed in step 1 (step 2); Immersing the aluminum alloy subjected to the secondary anodization treatment in step 2 in a 0.01-10M phosphoric acid (H ₃ PO ₄ ) solution for 38-42 minutes to expand pores (step 3); Tertiary anodizing the aluminum alloy for which pore expansion is completed in step 3 (step 4); And coating the aluminum alloy subjected to the third anodization in step 4 with a hydrophobic coating material (step 5), wherein the second anodization of step 2 and the third anodization of step 4 are each 38 Superhydrophobicity of a bundled pillar-on-pore structure, characterized by anodizing using mild anodizing conditions for anodizing at -42V for 28-32 minutes It provides a manufacturing method of 6000 series aluminum alloy anodizing film having a surface.

Furthermore, the present invention provides a 6000 series aluminum alloy having an anodized film having a superhydrophobic surface having a bundled pillar-on-pore structure manufactured by the above method.

In the method for manufacturing a 6000 series aluminum alloy anodizing film having a superhydrophobic surface of the present invention, the pore shape, diameter and density of the anodized aluminum layer formed on the aluminum alloy surface are determined by controlling the anodization voltage and time and pore expansion time. -By implementing it in the form of an on-pore, it has an economic effect of manufacturing an aluminum alloy with a controlled three-dimensional anodized film structure at low cost in a short time, and the anodized film structure manufactured by the above method is controlled. Aluminum alloy has excellent superhydrophobicity, corrosion resistance, durability, abrasion resistance, and thermal conductivity, so it is possible to use external cases for sensors, cutting blades for cutting tools, housing for electronic devices, lighting covers such as LEDs, heat exchangers, pipes, road structures, automobiles, aircraft, and ships. , It can be used in various industrial fields such as generators.

1 is a three-dimensional structure of a top view, a tilted view, and a cross view of an aluminum alloy anodized film formed on the prepatterned aluminum alloy surface of Examples 1 to 4 according to the present invention. This is a scanning electron microscope (SEM) image taken; At this time, MA was performed at 40V for 30 minutes, HA at 80V for 30 seconds, and PW at 30°C for 20 minutes, and the scale bars of the upper and transverse surfaces were 200 nm and 1 μm, respectively.
2 is a three-dimensional structure of a top view, a tilted view, and a cross view of an aluminum alloy anodized film formed on the prepatterned aluminum alloy surface of Examples 5 to 8 according to the present invention. This is a scanning electron microscope (SEM) image taken; At this time, MA was carried out at 40V for 30 minutes, HA at 80V for 30 seconds, and PW at 30°C for 30 minutes, the scale bar on the top surface was 200 nm, and the scale bars on the slopes and transverse surfaces were 500 nm and 1 μm, respectively.
3 is a three-dimensional structure of a top view, a tilted view, and a cross view of an aluminum alloy anodized film formed on the prepatterned aluminum alloy surface of Examples 9 to 12 according to the present invention. This is a scanning electron microscope (SEM) image taken; At this time, MA was carried out at 40V for 30 minutes, HA at 80V for 30 seconds, and PW at 30°C for 40 minutes, the scale bar on the top surface was 500 nm, and the scale bars on the slopes and the horizontal sides were respectively 500 nm and 1 μm.
4 is an image showing a result of measuring a contact angle with respect to a water droplet of an aluminum alloy anodized film formed on the prepatterned aluminum alloy surface of Examples 1 to 12 and Comparative Example 1 according to the present invention.

Hereinafter, the present invention will be described in detail.

Manufacturing method of 6000 series aluminum alloy anodizing film with superhydrophobic surface

The present invention is a pre-patterning step of removing the primary anodization film by etching after the first anodization treatment of 6000 series aluminum alloy at 30-50V for 5-15 hours (step 1) ;

Secondary anodizing the aluminum alloy for which pre-patterning has been completed in step 1 (step 2);

Pore widening the aluminum alloy subjected to the secondary anodization treatment in step 2 (step 3);

Tertiary anodizing the aluminum alloy for which pore expansion is completed in step 3 (step 4); And

Including; coating the aluminum alloy subjected to the third anodization in step 4 with a hydrophobic coating material (step 5),

The secondary anodization of step 2 is characterized in that the anodization is performed using a mild anodizing condition of anodizing at 30-50V for 15-45 minutes,

The pore expansion in step 3 is characterized in that the aluminum alloy subjected to the secondary anodization treatment in step 2 is immersed in a 0.01-10M phosphoric acid (H ₃ PO ₄ ) solution for 25-47 minutes,

The third anodization of step 4 may be performed under a mild anodizing condition of anodizing at 30-50V for 15-45 minutes; And hard anodizing conditions for anodizing at 70-90V for 15-45 seconds. Characterized in that the anodization treatment using any one of the conditions,

It provides a method for manufacturing a 6000 series aluminum alloy anodized film having a superhydrophobic surface.

In general, when water droplets come into contact with a solid surface, when the contact angle of the water droplet falls within the range of 120 to 150°, it is defined as hydrophobic, and when the contact angle is more than 150°, super hydrophobic, 170 Above ° is defined as ultra super hydrophobic.

In the method for producing a 6000 series aluminum alloy anodizing film having a superhydrophobic surface according to the present invention, a secondary anodized aluminum layer is formed by the secondary anodization, and the third anodized aluminum is formed by the third anodization. Layers can be formed. At this time, the area of the secondary anodized aluminum layer by secondary anodization is formed on the outside far from the surface of the aluminum alloy, and the area of the third anodized aluminum layer by the third anodization is formed on the inside close to the surface of the aluminum alloy. It can be.

In the method for producing a 6000 series aluminum alloy anodizing film having a superhydrophobic surface according to the present invention, preferably, the secondary anodization of step 2 is a soft anodization of anodizing at 35-45V for 20-40 minutes ( mild anodizing) conditions may be used to perform anodization treatment, and when anodizing is performed under the above conditions, a pillar-on-pore structure is formed on the surface of the aluminum alloy, thereby exhibiting superhydrophobicity. If it deviates, the pillar-on-pore structure is not formed (see Experimental Examples 1 to 3).

More preferably, the secondary anodization of step 2 may be anodization treatment using mild anodizing conditions of anodizing at 37-43V for 25-35 minutes, and anodizing under the above conditions. In the case of performing, a clearer pillar-on-pore structure is formed on the surface of the aluminum alloy, thereby exhibiting excellent superhydrophobicity (see Experimental Examples 1 to 3).

Even more preferably, the secondary anodization of step 2 may be anodizing treatment using a mild anodizing condition of anodizing at 38-42V for 28-32 minutes, and the anode In the case of oxidation, a bundle-type pillar structure is formed on the surface of the aluminum alloy, which has the effect of showing ultra-hydrophobicity. If it is out of the above range, a bundle-type pillar-on-pore structure is not formed, and a single-type pillar- An on-pore structure may be formed, or a pillar-on-pore structure may not be formed, and thus superaqueous properties may not appear (see Experimental Examples 1 to 3).

In the method for manufacturing a 6000 series aluminum alloy anodized film having a superhydrophobic surface according to the present invention, preferably, the pore expansion in step 3 may be immersion for 30-45 minutes, and pore expansion is performed under the above conditions. In this case, a pillar-on-pore structure is formed on the surface of the aluminum alloy to exhibit superhydrophobicity, and when it is out of the above condition range, a pillar-on-pore structure is not formed (see Experimental Examples 1 to 3).

More preferably, the pore expansion in step 3 may be immersed for 35-43 minutes, and when the pore expansion is performed under the above conditions, a clearer pillar-on-pore structure is formed on the surface of the aluminum alloy, resulting in excellent super There is an effect of showing hydrophobicity (see Experimental Examples 1 to 3).

Even more preferably, the pore expansion of the step 3 may be immersion for 38-42 minutes, and when the pore expansion is performed under the above conditions, a bundle-type pillar structure is formed on the surface of the aluminum alloy, indicating ultra-superhydrophobicity. If there is an effect, and out of the above condition range, a bundle-type pillar-on-por structure is not formed, a single type pillar-on-por structure may be formed, or a pillar-on-por structure is not formed. Water may not appear (see Experimental Examples 1 to 3).

In the method for producing a 6000 series aluminum alloy anodizing film having a superhydrophobic surface according to the present invention, preferably, the third anodization in step 4 is a soft anodization (a) that is anodized at 35-45V for 20-40 minutes. mild anodizing) conditions; And hard anodizing conditions for anodizing at 75-85V for 20-40 seconds. Anodizing treatment may be performed using any one of the conditions, and when anodizing is performed under the above conditions, a pillar-on-pore structure is formed on the surface of the aluminum alloy to exhibit superhydrophobicity, and the above condition range If it is out of the pillar-on-pore structure is not formed (see Experimental Examples 1 to 3).

More preferably, the third anodization of step 4 is performed under a mild anodizing condition of anodizing at 37-43V for 25-35 minutes; And hard anodizing conditions for anodizing at 77-83V for 25-35 seconds. Anodizing treatment may be performed using any one of the conditions, and when anodizing is performed under the above conditions, a clearer pillar-on-pore structure is formed on the surface of the aluminum alloy, thereby exhibiting excellent superhydrophobicity ( See Experimental Examples 1 to 3).

Even more preferably, the third anodization of step 4 may be anodization treatment using a mild anodizing condition of anodizing at 38-42V for 28-32 minutes, and the anode In the case of oxidation, a bundle-type pillar structure is formed on the surface of the aluminum alloy, which has the effect of showing ultra-hydrophobicity. If it is out of the above range, a bundle-type pillar-on-pore structure is not formed, and a single-type pillar- An on-pore structure may be formed, or a pillar-on-pore structure may not be formed, and thus superaqueous properties may not appear (see Experimental Examples 1 to 3).

In the 6000 series aluminum alloy anode oxide film manufacturing method having a superhydrophobic surface of the present invention, a hydrophobic coating material of step 5 is the surface energy is 6mJ / m ² to 20mJ / m ² is 1 to 20 fluorine the number of carbon chain Individual perfluoroalkylsilanes (e.g. 1 H ,1 H ,2 H ,2 H -perfluorodecyltrichlorosilane (FDTS), etc.) and alkylsilanes having 1 to 20 carbon atoms (e.g. trichlorooctylsilane ( OTS), octadecyltrichlorosilane (ODTS, etc.) may be to use one or more types of hydrophobic silane coating material selected from the group consisting of.

The aluminum alloy anodized film having a superhydrophobic surface according to the present invention may have a pillar-on-pore structure.

In the method for manufacturing a 6000 series aluminum alloy anodized film having a superhydrophobic surface according to the present invention, the pore diameter and pores of the three-dimensional anodic aluminum oxide layer formed on the aluminum alloy surface Superhydrophobicity may be expressed by controlling at least one of the interpore distances.

In the method for manufacturing a 6000 series aluminum alloy anodized film having a superhydrophobic surface according to the present invention, the control of the anodization film structure of the aluminum alloy surface is performed in which the pore diameter of the secondary anodized aluminum layer is It may be controlled to have a hierarchical structure larger than the diameter.

In the method for manufacturing a 6000 series aluminum alloy anodizing film having a superhydrophobic surface according to the present invention, the electrolyte in which the first anodization in step 1, the secondary anodization in step 2, and the third anodization in step 3 is performed is each Sulfuric acid (H ₂ SO ₄ ), phosphoric acid (H3PO4), oxalic acid (C ₂ H2O ₄ ), chromic acid, hydrofluoric acid, potassium hydrogen phosphate (dipotassium phosphate, K ₂ HPO ₄ ) can be used, or any one of a mixture thereof can be used, and a material on which the metal to be anodized is formed in the oxidation treatment tank containing the electrolyte is used as a working electrode, and then the anode is attached, and then platinum ( It may be formed by oxidizing a cathode by using a Pt) or carbon electrode as a counter electrode. Preferably, the electrolyte solution may be made at a temperature of -5 to 10°C using 0.1-0.5M oxalic acid as an electrolyte solution, more preferably 0.2-0.4M oxalic acid electrolyte and at a temperature of -2 to 2°C. have.

In the method for manufacturing a 6000 series aluminum alloy anodizing film having a superhydrophobic surface according to the present invention, the 6000 series aluminum alloy is Al 6005, Al 6005A, Al 6020, Al 6060, Al 6061, Al 6063, Al 6082 and Al 6262. It may be one or more selected from the group consisting of.

6000 series aluminum alloy with superhydrophobic surface anodized film

In addition, the present invention provides a 6000 series aluminum alloy having an anodic oxidation film having a superhydrophobic surface manufactured by the method for producing a 6000 series aluminum alloy anodizing film having a superhydrophobic surface.

The aluminum alloy according to the present invention may have a three-dimensional anodic aluminum oxide layer formed on its surface.

The aluminum alloy according to the present invention may have a pillar-on-pore structure.

Manufacturing method of 6000 series aluminum alloy anodizing film with superhydrophobic surface of bundled pillar-on-pore structure

In addition, the present invention is a pre-patterning step of removing the first anodized film by etching after the first anodization treatment of 6000 series aluminum alloy at 30-50V for 5-15 hours (step One);

Secondary anodizing the aluminum alloy for which pre-patterning has been completed in step 1 (step 2);

Immersing the aluminum alloy subjected to the secondary anodization treatment in step 2 in a 0.01-10M phosphoric acid (H ₃ PO ₄ ) solution for 38-42 minutes to expand pores (step 3);

Tertiary anodizing the aluminum alloy for which pore expansion is completed in step 3 (step 4); And

Including; coating the aluminum alloy subjected to the third anodization in step 4 with a hydrophobic coating material (step 5),

The second anodization of step 2 and the third anodization of step 4 are anodized using mild anodizing conditions of anodizing at 38-42V for 28-32 minutes, respectively. ,

It provides a method for manufacturing a 6000 series aluminum alloy anodizing film having a superhydrophobic surface of a bundled pillar-on-pore structure.

According to an embodiment of the present invention, if the voltage and time conditions of the second anodization of step 2 and the third anodization of step 4 and the pore expansion time condition of step 3 are out of range, the bundled pillar- An on-pore structure is not formed, a single-type pillar-on-pore structure may be formed, or a pillar-on-pore structure may not be formed, so that superaqueous properties may not appear (see Experimental Examples 1 to 3).

In the method for producing a 6000 series aluminum alloy anodizing film having a superhydrophobic surface of a bundled pillar-on-pore structure according to the present invention, preferably, the secondary anodization of the step 2 And the third anodization of step 4 may be anodization treatment using mild anodizing conditions of anodizing at 39-41V for 29-31 minutes, respectively, and anodizing may be performed under the above conditions. In this case, there is an effect that a more clear bundle-type pillar-on-pore structure is formed on the surface of the aluminum alloy to exhibit excellent ultra-hydrophobicity (see Experimental Examples 1 to 3).

In the method for manufacturing a 6000 series aluminum alloy anodizing film having a superhydrophobic surface of a bundled pillar-on-pore structure according to the present invention, preferably, the pore expansion in step 3 is 39 It may be immersed for -41 minutes, and when pore expansion is performed under the above conditions, a more clear bundle-type pillar-on-pore structure is formed on the surface of the aluminum alloy, thereby exhibiting excellent ultra-hydrophobicity (Experimental Example 1 To 3).

In the method for manufacturing a 6000 series aluminum alloy anodizing film having a superhydrophobic surface of a bundled pillar-on-pore structure according to the present invention, the hydrophobic coating material of step 5 has surface energy. 6mJ / m ² to 20mJ / m ² of a fluorocarbon chain the number of 1 to 20 perfluoroalkyl alkyl silane (such as: 1 H, 1 H, 2 H, 2 H - as decyl trichloro perfluorodecylmethacrylate silane (FDTS), etc.) And an alkylsilane having 1 to 20 carbon atoms (eg, trichlorooctylsilane (OTS), octadecyltrichlorosilane (ODTS), etc.). It may be to use at least one hydrophobic silane coating material selected from the group consisting of.

In the method for manufacturing a 6000 series aluminum alloy anodizing film having a superhydrophobic surface of a bundled pillar-on-pore structure according to the present invention, the secondary anodized aluminum by the secondary anodization A layer is formed, and a third anodized aluminum layer may be formed by the third anodization. At this time, the area of the secondary anodized aluminum layer by secondary anodization is formed on the outside far from the surface of the aluminum alloy, and the area of the third anodized aluminum layer by the third anodization is formed on the inside close to the surface of the aluminum alloy. It can be.

In the method for manufacturing a 6000 series aluminum alloy anodized film having a superhydrophobic surface having a bundled pillar-on-pore structure according to the present invention, the bundled pillar-on-pore on the aluminum alloy surface (Bundled pillar-on-pore) structure of the anodic aluminum oxide (anodic aluminum oxide) layer is formed, it may be that excellent ultra-hydrophobicity is expressed.

In the method for manufacturing a 6000 series aluminum alloy anodizing film having a superhydrophobic surface of a bundled pillar-on-pore structure according to the present invention, the first anodization of step 1, the step 2 The electrolytes in which the secondary anodic oxidation and the third anodic oxidation of step 3 are performed are sulfuric acid (H ₂ SO ₄ ), phosphoric acid (H ₃ PO ₄ ), oxalic acid (C ₂ H2O ₄ ), Any one of chromic acid, hydrofluoric acid, and potassium hydrogen phosphate (K ₂ HPO ₄ ) may be used, or any one of a mixture thereof may be used, and the anode in the oxidation treatment reactor containing the electrolyte solution It may be oxidized by attaching an anode using a material on which the metal to be oxidized is formed as a working electrode, and then attaching a cathode using a platinum (Pt) or carbon electrode as a counter electrode. Preferably, the electrolyte solution may be made at a temperature of -5 to 10°C using 0.1-0.5M oxalic acid as an electrolyte solution, more preferably 0.2-0.4M oxalic acid electrolyte and at a temperature of -2 to 2°C. have.

In the method for manufacturing a 6000 series aluminum alloy anodizing film having a superhydrophobic surface of a bundled pillar-on-pore structure according to the present invention, the 6000 series aluminum alloy is Al 6005, Al 6005A, Al 6020, Al 6060, Al 6061, Al 6063, Al 6082 and Al 6262 may be one or more selected from the group consisting of.

The method for manufacturing a 6000 series aluminum alloy anodization film having a superhydrophobic surface of a bundled pillar-on-pore structure of the present invention is a bundle type pillar-on-pore anode on an aluminum alloy surface. It has an economical effect of producing an oxide film in a short time at low cost.

6000 series aluminum alloy with anodized film with superhydrophobic surface of bundled pillar-on-pore structure

In addition, the present invention is a bundled pillar-on-pore (bundled pillar-on-pore) manufactured by a 6000 series aluminum alloy anodized film manufacturing method having a superhydrophobic surface having a structure of the bundle-type pillar-on-pore. We provide 6000 series aluminum alloys with anodized film having a superhydrophobic surface of -on-pore) structure.

In the present invention, the wettability to water of the 6000 series aluminum alloy having an anodized film having a superhydrophobic surface having a superhydrophobic surface of the bundled pillar-on-pore structure according to the present invention is very low and superhydrophobic ( Superhydrophobicity) was excellent, and it was confirmed that ultra superhydrophobicity can be expressed (see Experimental Examples 2 and 3).

The outer case for sensors and cutting blades of cutting tools including 6000 series aluminum alloys with an anodized film having a superhydrophobic surface of a bundled pillar-on-pore structure

Further, the present invention provides an external case for a sensor including a 6000 series aluminum alloy having an anodized film having a superhydrophobic surface of the bundled pillar-on-pore structure.

The sensor of the present invention refers to an element, device, and system for measuring by changing the state of an object to be measured into a physical or chemical quantity that is already known. For example, the presence or absence of an object, Position, current, voltage, resistance, electromagnetic induction, displacement, magnetism, angle, deformation, magnitude, force (torque), pressure, speed, weight, light, color, humidity, temperature, heat, gas, water level, sound, pollution, etc. It may be to detect, detect, classify, or measure, but is not limited thereto. Preferably, it may be a sensor used in an extreme environment. At this time, the extreme environment means an environment under extreme conditions such as ultrafast radiation, high radiation, extremely low light, high pressure, high temperature, cryogenic temperature, extremely dry, high humidity, and strong acidity, and deep sea, underwater, ocean, underground, desert, For example, places such as volcanoes, hydrothermal vents, atmosphere, dead sea, polar, space, etc.

In addition, the present invention provides a cutting blade of a cutting tool comprising a 6000 series aluminum alloy formed with an anodized film having a superhydrophobic surface of the bundled pillar-on-pore structure.

The cutting tool may be one or more selected from the group consisting of a razor, an epilator, a knife, scissors, a nail clipper, a fruit filler, and a saw. The razor may be in any one of a vibrating type (reciprocating type), a rotary type, and a manual type.

In addition, the present invention provides a vehicle wheel, vehicle engine, bicycle frame, and windows including 6000 series aluminum alloys with an anodized film having a superhydrophobic surface of the bundled pillar-on-pore structure. to provide.

Hereinafter, the present invention will be described in more detail by the following examples. However, the following examples are merely illustrative of the present invention, and the content of the present invention is not limited by the following examples.

< Example > Aluminum alloy anodization film manufacturing

To prepare an aluminum alloy anodized film, pre-patterning, pore widening (PW) and voltage modulation were performed using an aluminum 6061 alloy. Component information of the aluminum 6061 alloy (Al 6061, size 20×30mm) is as follows; Si 0.62%, Fe 0.33%, Cu 0.28%, Mg 0.90%, Mn 0.06%, Ti 0.02%, Zn 0.02%, Cr 0.17% and Al Balance.

step 1: primary Through anodization and chemical etching Pre-patterning fair

As a 6000 series aluminum (Al) alloy plate for manufacturing an anodized film, using an aluminum 6061 alloy (McMaster-Carr (Los Angeles, CA, USA) / 89015K961), to remove impurities on the surface of the aluminum 6061 alloy Washed by sonication in acetone and ethanol for 10 minutes. To obtain the surface roughness, the ultrasonically cleaned aluminum 6061 alloy was put in a mixed solution of ethanol and perchloric acid (Junsei, C ₂ H ₅ OH:HClO ₄ = 4:1 (v/v)) and a voltage of 20 V at room temperature (20° C.) Was applied to electrolytic polishing for 1 minute. It was confirmed that the surface of the aluminum alloy, which had been electropolished, was well reflected and the surface was flat.

The electrolytically polished aluminum 6061 alloy (thickness 1mm, size 20×30mm) was used as a working electrode, and a platinum (Pt) electrode was used as a cathode, and the two electrodes maintained a constant distance between poles at 5cm intervals. Secondary anodization was performed. The primary anodic oxidation was performed using 0.3M oxalic acid as an electrolyte, and a double beaker was used to maintain the electrolyte temperature constant at 0°C. In order to suppress the disturbance of stable oxide growth due to local temperature increase, the mixture was stirred at a constant speed, and the alumina layer was grown by performing the first anodization process for 6 hours by applying a voltage of 40V using a constant voltage method.

The alumina layer grown through the first anodization treatment was immersed in a solution of chromic acid (1.8 wt%) and phosphoric acid (6 wt%) at 65° C. for 10 hours and etched to remove the grown alumina layer. A pre-patterning process was performed.

Step 2- 4: secondary And the third anodization and pore expansion process

Specifically, in order to obtain a desired film structure on the surface of the aluminum 6061 alloy, after the pre-pattering was completed, secondary anodization, pore expansion, and third anodization were performed.

Specifically, the second and third anodic oxidation processes of Examples and Comparative Examples were performed under the same acid electrolyte conditions as the first anodization process of Step 1, and soft anodization (MA) using a relatively low voltage of 40V. ) Or by using two techniques of hard anodization (HA) using a high voltage of 80V, anodization was performed by selectively controlling the magnitude and sequence of voltages applied during the secondary and tertiary anodization. At this time, the soft anodization was performed at 40V for 30 minutes, and the hard anodization was performed at 80V for 30 seconds. On the other hand, in the second and third anodization processes of Comparative Example 2, the applicant can form a pillar-on-pore type anodization layer on the surface of a 5000 series aluminum alloy through previous research. Anodization was performed using the conditions shown in Table 1 below.

In addition, the alumina layer grown through the second anodization is subjected to a pore widening (PW) process in which the alumina layer is immersed in a 0.1M phosphoric acid solution at 30°C for 20 to 60 minutes before performing the third anodization, Third anodization was performed to grow an aluminum anodized film.

Examples 1 to 1 in which the secondary anodization (step 2), pore expansion (step 3), and the third anodization (step 4) processes were performed under the conditions shown in Table 1 below, and the structural shape of the surface of the aluminum 6061 alloy was controlled. The aluminum alloy anodized films of 12 and Comparative Examples 1 to 2 were obtained.

Pre-patterning or not
(Step 1) Process mode
(Step 2-4) Secondary anodization
(Step 2) Pore Expansion (Step 3) 3rd anodization
(Step 4) Voltage(V) Time(min) Time(min) Voltage(V) Time(min) Example 1 Perform MA→PW→MA 40 30 20 40 30 Example 2 Perform MA→PW→HA 40 30 20 80 0.5 Example 3 Perform HA→PW→MA 80 0.5 20 40 30 Example 4 Perform HA→PW→HA 80 0.5 20 80 0.5 Example 5 Perform MA→PW→MA 40 30 30 40 30 Example 6 Perform MA→PW→HA 40 30 30 80 0.5 Example 7 Perform HA→PW→MA 80 0.5 30 40 30 Example 8 Perform HA→PW→HA 80 0.5 30 80 0.5 Example 9 Perform MA→PW→MA 40 30 40 40 30 Example 10 Perform MA→PW→HA 40 30 40 80 0.5 Example 11 Perform HA→PW→MA 80 0.5 40 40 30 Example 12 Perform HA→PW→HA 80 0.5 40 80 0.5 Comparative Example 1 Perform MA→PW→MA 40 30 60 40 30 Comparative Example 2 Perform HA→PW→HA 80 0.5 60 80 0.5

Step 5: surface coating process

Each of the porous aluminum alloy anodized films of Examples 1 to 12 and Comparative Examples 1 to 2 was SAM using 1 H , 1 H , 2 H , 2 H -perfluorodecyltrichlorosilane (FDTS), which is a coating material having low surface energy for 24 hours in a vacuum chamber. (Self-Assembled Monolayer) was coated to obtain an aluminum alloy anodized film having a hydrophobic surface. At this time, before coating with FDTS, the organic residue remaining on the anodized film is removed and the surface is made hydrophilic, and the coating material is washed for 15 minutes using oxygen plasma to increase the adhesion of the coating material, and then dried in the air. Then, baking was performed at 150°C for 10 minutes. Then, coating was performed in a vacuum using FDTS for 24 hours to obtain porous aluminum alloy anodized films of Examples 1 to 12 and Comparative Examples 1 to 2 having a hydrophobic surface.

< Experimental example 1> Structural characteristics analysis of aluminum alloy anodizing film according to 2nd and 3rd anodization conditions (voltage and time) and pore expansion time

As shown in Table 1, Examples 1 to 12 prepared by performing various modes of MA→PW→MA, MA→PW→HA, HA→PW→HA and HA→PW→MA and varying the pore expansion time. The surface and cross-sectional shape of the porous aluminum alloy anodized film was observed using a field emission scanning electron microscope (FE-SEM) system (AURIGA® small dual-bean FIB-SEM, Zeiss).

Each aluminum alloy anodized film specimen was cut into small pieces, fixed on a stage with carbon tape, coated with gold (Au) for 15 seconds by sputtering, and then imaged with a scanning electron microscope (SEM). At this time, the film specimen was bent at 90° to generate parallel cracks to observe the surface and cross-sectional structures of the aluminum alloy anodized film, as shown in FIGS. 1 to 4.

1 is a three-dimensional structure of a top view, a tilted view, and a cross view of an aluminum alloy anodized film formed on the prepatterned aluminum alloy surface of Examples 1 to 4 according to the present invention. This is a scanning electron microscope (SEM) image taken; At this time, MA was performed at 40V for 30 minutes, HA at 80V for 30 seconds, and PW at 30°C for 20 minutes, and the scale bars of the upper and transverse surfaces were 200 nm and 1 μm, respectively.

2 and 3 are a top view, a tilted view, and a cross-section of an aluminum alloy anodizing film formed on the prepatterned aluminum alloy surface of Examples 5 to 8 and 9 to 12 according to the present invention, respectively. This is a scanning electron microscope (SEM) image of a three-dimensional structure (cross view); At this time, MA was carried out at 40V for 30 minutes, HA at 80V for 30 seconds, and PW at 30°C for 30 minutes or 40 minutes, and the scale bar on the top surface was 200 nm or 500 nm, and the scale bars on the slopes and transverse surfaces. (scale bar) is 500nm and 1㎛, respectively.

As shown in FIGS. 1 to 3, in most cases, a result of increasing the diameter of the pores in the secondary anodization region of the aluminum alloy anodization film by the PW process was found, but the structure of the third anodization region Did not affect. Accordingly, since the sizes of the pores in the secondary anodization region and the tertiary anodization region are different in all Examples 1 to 12, the criteria for the secondary and tertiary anodization regions can be classified by the size transition of the pores. It was confirmed that this was formed hierarchically. In addition, it was found that the voltage type of the anodized film containing HA has a larger pore diameter and the gap between the pores and the pores than the voltage type of the anodized film containing MA. From these results, it was confirmed that the size of the anodization voltage can affect the size of the pores.

On the other hand, as shown in Figs. 2 and 3, Examples 5, 6, 9 and Examples 5, 6 and 9 prepared by performing pore expansion (PW) for 30 minutes or 40 minutes in MA→PW→MA mode or MA→PW→HA mode. In the case of 10, in the cross-view image, aligned straight pores are formed in the third anodization region of the lower part, and the tip-like structure is formed in the second anodization region of the straight pores. It was confirmed that it was formed. In the top view image, it was found that white (light gray) anodized oxide was formed next to the pores shown in black, and that part was a tip-like structure part formed in the secondary anodization region. Confirmed.

In the case of Examples 5, 6 and 10, in the case of Example 9, unlike other examples, anodization of a structure having a pillar-on-pore shape in which pillars are formed on a pore structure It was confirmed that the film was prepared, and in particular, it was confirmed that a much clearer pillar-on-pore shape was exhibited when prepared under the conditions of Example 9.

On the other hand, when manufactured under the conditions of Example 9, a bundle-shaped pillar was formed, and when manufactured under the conditions of Examples 5, 6, and 10, it was confirmed that a single-shaped pillar was formed.

When the anodized film having a pillar-on-pore structure is formed as described above, superhydrophobicity may be implemented on the surface of the aluminum alloy. At this time, when an aluminum alloy with a pillar-on-pore type film is used in industry, as the period of use increases, the pillar portion wears out and disappears, and the pore portion is exposed, resulting in deterioration of the superhydrophobic properties, and the shape of the pillar becomes a bundle. ) In the case of the shape, since the pillar structure is in a united form, the wear rate is significantly reduced compared to the single-shaped pillar, thereby improving durability.

On the other hand, in the case of Comparative Examples 1 and 2, the bundle-type pillar-on-pore structure did not appear at all, and the anode oxide having a single-type pillar-on-pore structure or a tip-like structure was not formed. Therefore, it was confirmed that the conditions for forming the pillar-on-pores structure were different according to the types of aluminum alloys of 5000 series and 6000 series.

As a result, not only the secondary and tertiary anodization voltage magnitude, which is a parameter, but also the pore expansion treatment time directly affects the pore size and controls the pore diameter and the gap between pores and pores, as well as the three-dimensional shape. It was confirmed that the growth of the aluminum anodized film of Example 9 can be controlled, and the POP structure in which the conditions of MA (40V, 30min) → PW (40min) → MA (40V, 30min) of Example 9 are the most clear, especially the bundled pillar- It was confirmed that it was a condition for producing an anodized film having a fillar bundle-on-pore structure.

< Experimental example 2> 2nd and 3rd anodic oxidation conditions (voltage and time) and pore expansion time Water repellency Characterization

In order to confirm the effect of the structural shape of the aluminum alloy anodized film on the water repellency property, the wettability to water was evaluated.

Using the contact angle measurement method to evaluate the wettability of the surfaces of the porous aluminum alloy anodized film structures of Examples 1 to 12 and Comparative Examples 1 to 2 coated with FDTS, the contact angle of 3 μl of deionized water droplets was measured at room temperature. Analyzed. In addition, the contact angle was measured by the same method using the FDTS coated on the surface of the aluminum alloy not subjected to anodization treatment as a control. The average value was calculated by measuring the contact angle at different places for each specimen at least five times, and the results are shown in Table 2 and FIG. 4 below.

Process mode
(Step 2-4) Contact angle(°) Control - 114.3±0.74 Example 1 MA→PW(20min)→MA 101.1±0.68 Example 2 MA→PW(20min)→HA 125.5±0.94 Example 3 HA→PW(20min)→MA 127.3±0.24 Example 4 HA→PW(20min)→HA 129.0±1.09 Example 5 MA→PW(30min)→MA 158.5±1.04 Example 6 MA→PW(30min)→HA 136.3±0.86 Example 7 HA→PW(30min)→MA 130.6±0.23 Example 8 HA→PW(30min)→HA 131.7±0.42 Example 9 MA→PW(40min)→MA 172.2±1.22 Example 10 MA→PW(40min)→HA 157.8±0.36 Example 11 HA→PW(40min)→MA 129.6±1.02 Example 12 HA→PW(40min)→HA 149.7±1.60 Comparative Example 1 MA→PW(60min)→MA 124.8±1.37 Comparative Example 2 HA→PW(60min)→HA 120.7±0.64

As shown in Table 2, the porous aluminum alloy anodized film of Examples 1 to 12 and Comparative Examples 1 to 2 prepared through MA and HA mode control and pore expansion time control in the second and third anodization processes When FDTS, which is a material having a low surface energy, was coated on, it was confirmed that the wettability to water was lower than when FDTS was coated on an aluminum alloy base material (control) not subjected to anodization.

On the other hand, in the case of the porous aluminum alloy anodizing film of Comparative Examples 1 and 2, the wettability was lower than that of the case where the anodization was not performed, but except for some examples of the present invention, examples according to the present invention It was found to be higher than that of 1 to 2 porous aluminum alloy anodized films.

In addition, the surface coated with FTDS on the porous aluminum alloy anodized film of Examples 5, 9 and 10 confirmed to be in the form of pillar-on-pores in Experimental Example 1 was found to have a contact angle of 150° or more. It was found that wettability to water was low compared to yes, and it was confirmed that it exhibits excellent superhydrophobicity (super water repellency). In particular, the surface coated with FTDS on the porous aluminum alloy anodized film of Example 9 prepared in the order of MA→PW(40min)→MA exhibited the most excellent superhydrophobicity, and showed a contact angle of 170° or more, so ultra-superhydrophobic super hydrophobic) was implemented.

These results show that the diameter of pores and the control of the gap between pores and pores by controlling the HA (80V) mode and MA (40V) mode in the second and third anodic oxidation processes and the time adjustment in the pore expansion process are It means that it has an effect on the wettability of the pillar-on-pores, and that the superhydrophobicity can be further improved when the shape of the pillar-on-pores is a bundle type rather than a single type. Secondary and third anodization conditions (MA) and pore expansion time (40min) used to prepare the porous aluminum alloy anodization film of Example 9 having a bundle-type pillar-on-pore structure of the present invention were superhydrophobic. It was confirmed that this is an optimal condition for implementation.

<Experimental Example 3> Confirmation of structural characteristics according to optimal condition control for realizing superhydrophobicity of aluminum alloy anodized film

Based on the conditions of Example 9 identified as the optimum condition for implementing superhydrophobicity in the porous aluminum alloy anodizing film in Experimental Examples 1 to 2, the voltage and time of the second anodization step, the pore expansion time, and the third order The voltage and time conditions of the anodization were further subdivided, and the structural characteristics were confirmed accordingly.

3-1. Structure of aluminum anodized film according to secondary anodization voltage condition

First, an aluminum alloy anodization film was prepared in the same manner as in Example 9, but the voltage level of the second anodization step (step 2) was changed under the conditions shown in Table 3 below, and Examples 13-1 to 13-6 An aluminum alloy anodized film was obtained. Example 9 and each of the aluminum alloy anodized films obtained by the above method were observed in the same manner as in Experimental Example 1 to observe the surface and cross-sectional structures to confirm whether a pillar-on-pore structure was formed and whether a bundle-shaped pillar was formed. Thus, it is shown together in Table 3 below.

Secondary anodization
(Step 2) Pore expansion
(Step 3) 3rd anodization
(Step 4) Whether pillar-on-pores are formed Formation of bundled pillars Voltage(V) Time(min) Time(min) Voltage(V) Time(min) Example 13-1 35 30 40 40 30 O X Example 13-2 37 30 40 40 30 O X Example 13-3 38 30 40 40 30 O O Example 9 40 30 40 40 30 O O Example 13-4 42 30 40 40 30 O O Example 13-5 43 30 40 40 30 O X Example 13-6 45 30 40 40 30 O X

As shown in Table 3, as a result of performing different voltage conditions of the secondary anodization at 35 to 45V, all pillar-on-pores structures were formed, but in the case of Examples 13-1 and 13-6, pillars The structure was not clearly formed, and it was found that a clearer pillar structure was formed in the aluminum anodized film prepared under the conditions of Examples 13-2 to 13-5 and Example 9. On the other hand, in the case of the bundled pillar structure, it was formed only under the voltage condition of 38 to 42V in Examples 13-3, 9 and 13-4, and in particular, in the aluminum anodized film prepared under the conditions of Example 9 It was confirmed that the most obvious bundle-type pillar-on-pore structure was formed.

3-2. Structure of aluminum anodized film according to secondary anodization time condition

First, an aluminum alloy anodization film was prepared in the same manner as in Example 9, but the time length of the second anodization step (step 2) was changed under the conditions shown in Table 4 below, and Examples 14-1 to 14-6 An aluminum alloy anodized film was obtained. Example 9 and each of the aluminum alloy anodized films obtained by the above method were observed in the same manner as in Experimental Example 1 to observe the surface and cross-sectional structures to confirm whether a pillar-on-pore structure was formed and whether a bundle-shaped pillar was formed. Thus, it is shown together in Table 4 below.

Secondary anodization
(Step 2) Pore expansion
(Step 3) 3rd anodization
(Step 4) Whether pillar-on-pores are formed Formation of bundled pillars Voltage(V) Time(min) Time(min) Voltage(V) Time(min) Example 14-1 40 20 40 40 30 O X Example 14-2 40 25 40 40 30 O X Example 14-3 40 28 40 40 30 O O Example 9 40 30 40 40 30 O O Example 14-4 40 32 40 40 30 O O Example 14-5 40 35 40 40 30 O X Example 14-6 40 40 40 40 30 O X

As shown in Table 4, as a result of varying the voltage condition of the secondary anodization from 20 to 40 minutes, all pillar-on-pores structures were formed, but in Examples 14-1 and 14-6, pillars The structure was not clearly formed, and it was found that a clearer pillar structure was formed in the aluminum anodized film prepared under the conditions of Examples 14-2 to 14-5 and Example 9. On the other hand, in the case of the bundled pillar structure, it was formed only under the conditions of 28 to 32 minutes in Examples 14-3, 9 and 14-4, and in particular, an aluminum anodized film prepared under the conditions of Example 9 It was confirmed that the most obvious bundle-type pillar-on-pore structure was formed.

3-3. Aluminum anodized film structure according to pore expansion time conditions

First, an aluminum alloy anodizing film was prepared in the same manner as in Example 9, but the time length of the pore expansion step (step 3) was changed under the conditions shown in Table 5 below, and the aluminum of Examples 15-1 to 15-8 An alloy anodized film was obtained. Examples 1, 5 and 9 and each aluminum alloy anodized film obtained by the above method were observed in the same manner as in Experimental Example 1 to observe the surface and cross-sectional structure, and whether a pillar-on-pore structure was formed and a bundle-shaped pillar Formation was confirmed and shown together in Table 5 below.

Secondary anodization
(Step 2) Pore expansion
(Step 3) 3rd anodization
(Step 4) Whether pillar-on-pores are formed Formation of bundled pillars Voltage(V) Time(min) Time(min) Voltage(V) Time(min) Example 15-1 40 30 10 40 30 X X Example 1 40 30 20 40 30 X X Example 5 40 30 30 40 30 O X Example 15-2 40 30 35 40 30 O X Example 15-3 40 30 37 40 30 O X Example 15-4 40 30 38 40 30 O O Example 9 40 30 40 40 30 O O Example 15-5 40 30 42 40 30 O O Example 15-6 40 30 43 40 30 O X Example 15-7 40 30 45 40 30 O X Example 15-8 40 30 50 40 30 X X

As shown in Table 5, as a result of varying the pore expansion time to 10 to 50 minutes, the pillar-on-por structure only in Examples 5, 9 and 15-2 to 15-7 in which the pore expansion was performed for 30 to 45 minutes Was formed. At this time, in the case of Examples 5 and 15-7, the pillar structure was not clearly formed, and in the aluminum anodized film prepared under the conditions of Examples 15-3 to 15-5 and Example 9, a more clear pillar structure was Appeared to be formed. Meanwhile, in the case of a bundled pillar structure, it was formed only under the conditions of 38 to 42 minutes in Examples 15-4, 9 and 15-5, and in particular, in the aluminum anodized film prepared under the conditions of Example 9 It was confirmed that the most obvious bundle-type pillar-on-por structure was formed.

3-4. Structure of aluminum anodized film according to the third anodization voltage condition

First, an aluminum alloy anodizing film was prepared in the same manner as in Example 9, but the voltage level of the third anodization step (step 4) was changed under the conditions shown in Table 6 below, and Examples 16-1 to 16-6 An aluminum alloy anodized film was obtained. Example 9 and each of the aluminum alloy anodized films obtained by the above method were observed in the same manner as in Experimental Example 1 to observe the surface and cross-sectional structures to confirm whether a pillar-on-pore structure was formed and whether a bundle-shaped pillar was formed. Thus, it is shown in Table 6 together.

Secondary anodization
(Step 2) Pore expansion
(Step 3) 3rd anodization
(Step 4) Whether pillar-on-pores are formed Formation of bundled pillars Voltage(V) Time(min) Time(min) Voltage(V) Time(min) Example 16-1 40 30 40 35 30 O X Example 16-2 40 30 40 37 30 O X Example 16-3 40 30 40 38 30 O O Example 9 40 30 40 40 30 O O Example 16-4 40 30 40 42 30 O O Example 16-5 40 30 40 43 30 O X Example 16-6 40 30 40 45 30 O X

As shown in Table 6, as a result of performing different voltage conditions of the third anodization at 35 to 45V, all pillar-on-pore structures were formed, but in the case of Examples 16-1 and 16-6, pillars The structure was not clearly formed, and it was found that a clearer pillar structure was formed in the aluminum anodized film prepared under the conditions of Examples 16-2 to 16-5 and Example 9. On the other hand, in the case of the bundled pillar structure, it was formed only under a voltage condition of 38 to 42V in Examples 16-3, 9 and 16-4, and in particular, in the aluminum anodized film prepared under the conditions of Example 9 It was confirmed that the most obvious bundle-type pillar-on-por structure was formed.

3-5. Structure of aluminum anodized film according to 3rd anodization time condition

First, an aluminum alloy anodizing film was prepared in the same manner as in Example 9, but the time length of the third anodizing step (step 4) was changed under the conditions shown in Table 7 below, and Examples 17-1 to 17-6 An aluminum alloy anodized film was obtained. Example 9 and each of the aluminum alloy anodized films obtained by the above method were observed in the same manner as in Experimental Example 1 to observe the surface and cross-sectional structures to confirm whether a pillar-on-pore structure was formed and whether a bundle-shaped pillar was formed. Thus, it is shown in Table 7 together.

Secondary anodization
(Step 2) Pore expansion
(Step 3) 3rd anodization
(Step 4) Whether pillar-on-pores are formed Formation of bundled pillars Voltage(V) Time(min) Time(min) Voltage(V) Time(min) Example 17-1 40 30 40 40 20 O X Example 17-2 40 30 40 40 25 O X Example 17-3 40 30 40 40 28 O O Example 9 40 30 40 40 30 O O Example 17-4 40 30 40 40 32 O O Example 17-5 40 30 40 40 35 O X Example 17-6 40 30 40 40 40 O X

As shown in Table 7 above, as a result of varying the voltage condition of the secondary anodization from 20 to 40 minutes, all pillar-on-pores structures were formed, but in Examples 17-1 and 17-6, pillars The structure was not clearly formed, and it was found that a clearer pillar structure was formed in the aluminum anodized film prepared under the conditions of Examples 17-2 to 17-5 and Example 9. On the other hand, in the case of a bundled pillar structure, it was formed only under the conditions of 28 to 32 minutes in Examples 17-3, 9 and 17-4, and in particular, an aluminum anodized film prepared under the conditions of Example 9 It was confirmed that the most obvious bundle-type pillar-on-pore structure was formed.

So far, the present invention has been looked at around its preferred embodiments. Those of ordinary skill in the art to which the present invention pertains will be able to understand that the present invention can be implemented in a modified form without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments should be considered from an illustrative point of view rather than a limiting point of view. The scope of the present invention is shown in the claims rather than the foregoing description, and all differences within the scope equivalent thereto should be construed as being included in the present invention.

Claims (16)

A pre-patterning step (step 1) of performing primary anodization treatment of 6000 series aluminum alloy at 30-50V for 5-15 hours, and then etching to remove the primary anodization film;
Secondary anodizing the aluminum alloy pre-patterned in step 1 at 37-43V for 25-35 minutes (step 2);
Immersing the aluminum alloy subjected to the secondary anodization treatment in step 2 in a 0.01-10M phosphoric acid (H ₃ PO ₄ ) solution for 29-31 minutes or 37-42 minutes to expand pores (step 3);
3rd anodizing the aluminum alloy for which pore expansion is completed in step 3 at 37-43V for 25-35 minutes or at 78-82V for 25-35 seconds (step 4); And
Including; coating the aluminum alloy subjected to the third anodization treatment in step 4 with a hydrophobic coating material (step 5),
When the immersion time in step 3 is 29-31 minutes, the third anodization treatment is performed at 37-43V for 25-35 minutes in step 4, and
When the immersion time in step 3 is 37-42 minutes, the third anodization treatment is performed at 37-43V for 25-35 minutes in step 4, and
When the immersion time in step 3 is 37-42 minutes, the third anodization treatment is performed at 78-82V for 25-35 seconds in step 4,
A method for manufacturing a 6000 series aluminum alloy anodized film having a superhydrophobic surface of a bundled pillar-on-pore structure.
delete delete delete delete delete delete delete The method of claim 1,
The 6000 series aluminum alloy is a 6000 series having a superhydrophobic surface, characterized in that at least one selected from the group consisting of Al 6005, Al 6005A, Al 6020, Al 6060, Al 6061, Al 6063, Al 6082 and Al 6262 Method for producing an aluminum alloy anodized film.
A 6000 series aluminum alloy having an anodic oxide film having a superhydrophobic surface having a bundled pillar-on-pore structure manufactured by the method of claim 1.
delete A pre-patterning step (step 1) of performing primary anodization treatment of 6000 series aluminum alloy at 30-50V for 5-15 hours, and then etching to remove the primary anodization film;
Secondary anodizing the aluminum alloy pre-patterned in step 1 at 38-42V for 28-32 minutes (step 2);
Immersing the aluminum alloy subjected to the secondary anodization treatment in step 2 in a 0.01-10M phosphoric acid (H ₃ PO ₄ ) solution for 38-42 minutes to expand pores (step 3);
Performing a third anodization treatment of the aluminum alloy having pore expansion completed in step 3 at 38-42V for 28-32 minutes (step 4); And
Including; coating the aluminum alloy subjected to the third anodization treatment in step 4 with a hydrophobic coating material (step 5);
A method for producing a 6000 series aluminum alloy anodizing film having a superhydrophobic surface of a bundled pillar-on-pore structure.
A 6000 series aluminum alloy with an anodized film having a superhydrophobic surface having a bundled pillar-on-pore structure manufactured by the method of claim 12.
An external case for a sensor comprising a 6000 series aluminum alloy having an anodized film having a superhydrophobic surface having a bundled pillar-on-pore structure of claim 12.
The cutting blade of a cutting tool comprising a 6000 series aluminum alloy formed with an anodized film having a superhydrophobic surface having a bundled pillar-on-pore structure of claim 12.
A vehicle wheel comprising a 6000 series aluminum alloy formed with an anodized film having a superhydrophobic surface having a bundled pillar-on-pore structure of claim 12.

Images