WO2021096226A1 - Procédé d'amélioration de la mise en œuvre d'une couleur vive sur une surface superhydrophile d'alliage d'aluminium - Google Patents

Procédé d'amélioration de la mise en œuvre d'une couleur vive sur une surface superhydrophile d'alliage d'aluminium Download PDF

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WO2021096226A1
WO2021096226A1 PCT/KR2020/015809 KR2020015809W WO2021096226A1 WO 2021096226 A1 WO2021096226 A1 WO 2021096226A1 KR 2020015809 W KR2020015809 W KR 2020015809W WO 2021096226 A1 WO2021096226 A1 WO 2021096226A1
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aluminum alloy
anodization
anodizing
dyeing
minutes
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정찬영
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동의대학교 산학협력단
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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
    • C25D11/12—Anodising more than once, e.g. in different baths
    • 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
    • C25D11/022—Anodisation on selected surface areas
    • 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
    • C25D11/24—Chemical after-treatment
    • 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
    • C25D11/24—Chemical after-treatment
    • C25D11/243—Chemical after-treatment using organic dyestuffs
    • 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
    • C25D11/24—Chemical after-treatment
    • C25D11/246—Chemical after-treatment for sealing layers

Definitions

  • the present invention relates to a method for dyeing an aluminum alloy for realizing uniform and vivid colors, and more particularly, to a method for dyeing an aluminum alloy by forming a superhydrophilic aluminum alloy surface.
  • 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 being conducted.
  • 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.
  • this anodized film has a two-dimensional porous arrangement that can control only the side dimensions.
  • many studies and technologies such as the aquatic acid method, the sulfuric acid method, and the phosphoric acid method have been developed, but the change in the type and concentration of the acid electrolyte.
  • the anodization 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.
  • 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, has a lower contact angle than the conventional planar hexagonal porous surface. contact angle) and high contact angle hysteresis, and thus has excellent superhydrophilic properties.
  • the applicant of the present invention solved the conventional problems as described above, and in order to develop an aluminum alloy dyeing method with excellent uniformity, clarity and durability of the dyed color, the anodic oxidation voltage of the pre-patterned aluminum alloy
  • the present invention was completed by confirming that the anodic oxidation film of the hierarchical structure produced by controlling the 2nd and 3rd anodic oxidation process and controlling the pore expansion time exhibits excellent superhydrophilicity and enables uniform and clear dyeing. I did.
  • An object of the present invention is to provide a method for dyeing an aluminum (Al) alloy.
  • Another object of the present invention is to provide an aluminum alloy dyed by the above method.
  • the present invention is a pre-patterning step (step 1) of removing the first anodized film by etching after first anodizing an aluminum alloy at 30-50V for 5-15 hours;
  • step 2 Secondary anodizing the aluminum alloy for which pre-patterning has been completed in step 1 (step 2);
  • step 3 Pore widening the aluminum alloy subjected to the secondary anodization treatment in step 2 (step 3);
  • step 5 Including; dyeing the aluminum alloy subjected to the third anodization treatment in step 4 with a dye (step 5),
  • step 2 The secondary anodization of step 2 is characterized in that the anodization treatment is performed using hard anodizing conditions of anodizing at 70-90V for 20-40 seconds,
  • step 3 The pore expansion of step 3 is characterized in that the aluminum alloy subjected to the secondary anodization treatment of step 2 is immersed in a 0.01-10M phosphoric acid (H 3 PO 4 ) solution for 25-65 minutes,
  • the third anodization of step 4 is characterized in that the anodization treatment is performed using a mild anodizing condition of anodizing at 30-50V for 20-40 minutes, respectively,
  • the present invention provides an aluminum alloy dyed by the above method.
  • the aluminum alloy dyeing method according to the present invention implements the pore shape, diameter, and density of the anodized aluminum layer formed on the aluminum alloy surface in the form of a hierarchical structure showing superhydrophilicity through control of anodization conditions and pore expansion time. By doing so, it has the effect of facilitating the coloring of hydrophilic dyes and shortening the dyeing time, and has excellent dyeing uniformity, color clarity, and durability, and thus, electronic housings, lighting covers such as LEDs, heat exchangers, pipes, road structures, automobiles, etc. It can be used in a variety of industrial fields that require exterior color implementation such as aircraft, ships, and generators.
  • Example 1 is a process chart showing a step of manufacturing an aluminum alloy anodizing film having a hierarchical structure of Example 3 according to the present invention.
  • FIG. 2 is a scanning electron microscope photographing a three-dimensional structure of an aluminum alloy anodized film formed on the prepatterned aluminum alloy surface of Examples 1 to 4 according to the present invention (top view) and cross-section ( SEM) is an image; 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, and the scale bars of the surface and cross-section were 200 nm and 1 ⁇ m, respectively.
  • FIG. 3 is a scanning electron microscope photographing a three-dimensional structure of an aluminum alloy anodized film formed on the prepatterned aluminum alloy surface of Examples 5 to 8 according to the present invention (top view) and cross-section ( SEM) is an image; At this time, MA was performed at 40V for 30 minutes, HA at 80V for 30 seconds, and PW at 30°C for 40 minutes, and the scale bars of the surface and cross-section were 200 nm and 1 ⁇ m, respectively.
  • FIG. 4 is a scanning electron microscope photographing a three-dimensional structure of an aluminum alloy anodized film formed on the prepatterned aluminum alloy surface of Examples 9 to 12 according to the present invention (top view) and cross-section ( SEM) is an image; At this time, MA was performed at 40V for 30 minutes, HA at 80V for 30 seconds, and PW at 30°C for 50 minutes, and the scale bars of the surface and cross-section were 200 nm and 1 ⁇ m, respectively.
  • FIG. 5 is a scanning electron microscope photographing a three-dimensional structure of an aluminum alloy anodizing film formed on the prepatterned aluminum alloy surface of Examples 13 to 16 according to the present invention (top view) and cross-section ( SEM) is an image; At this time, MA was carried out at 40V for 30 minutes, HA at 80V for 30 seconds, and PW at 30°C for 60 minutes, and the scale bars of the surface and cross-section were 200 nm and 1 ⁇ m, respectively.
  • FIG 6 is an image showing the result of measuring the contact angle with respect to the water droplets of the aluminum alloy anodized film formed on the prepatterned aluminum alloy surface of Examples 1 to 4 according to the present invention.
  • FIG 7 is an image showing the result of measuring the contact angle with respect to the water droplets of the aluminum alloy anodized film formed on the prepatterned aluminum alloy surface of Examples 13 to 16 according to the present invention.
  • the present invention is a pre-patterning step (step 1) of removing the first anodized film by etching after first anodizing an aluminum alloy at 30-50V for 5-15 hours;
  • step 2 Secondary anodizing the aluminum alloy for which pre-patterning has been completed in step 1 (step 2);
  • step 3 Pore widening the aluminum alloy subjected to the secondary anodization treatment in step 2 (step 3);
  • step 5 Including; dyeing the aluminum alloy subjected to the third anodization treatment in step 4 with a dye (step 5),
  • step 2 The secondary anodization of step 2 is characterized in that the anodization treatment is performed using hard anodizing conditions of anodizing at 70-90V for 20-40 seconds,
  • step 3 The pore expansion of step 3 is characterized in that the aluminum alloy subjected to the secondary anodization treatment of step 2 is immersed in a 0.01-10M phosphoric acid (H 3 PO 4 ) solution for 25-65 minutes,
  • the third anodization of step 4 is characterized in that the anodization treatment is performed using a mild anodizing condition of anodizing at 30-50V for 20-40 minutes, respectively,
  • a secondary anodized aluminum layer may be formed by the secondary anodization, and a third anodized aluminum layer may be formed by the tertiary anodization.
  • the area of the secondary anodized aluminum layer by secondary anodization is formed on the outer side 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.
  • the pore diameter and pore distance are controlled by the conditions of the secondary anodization and pore expansion process, and the third anodized aluminum layer region is formed by the third anodization process conditions.
  • the diameter and spatial distance of are controlled.
  • the aluminum alloy according to the present invention may exhibit superhydrophilicity by controlling the structure of the anodized film formed on the surface.
  • the secondary anodization of the step 2 is anodized using a hard anodizing condition of anodizing at 75-85V for 25-35 seconds
  • the third anodization of step 4 may be anodization treatment using a soft anodization condition of anodizing at 25-35V for 25-35 minutes.
  • the secondary anodization of step 2 is anodized using a hard anodizing condition of anodizing at 78-82V for 28-32 seconds, and the third anodizing of step 4 is 28-32V. It may be anodizing using soft anodizing conditions for anodizing at 28-32 minutes.
  • a layered structure capable of showing ultra-superhydrophilicity is formed on the surface of the aluminum alloy, thereby further improving dyeing uniformity and color clarity.
  • ultra superhydrophilicity may not appear (see Experimental Examples 1 to 2).
  • the secondary anodization of step 2 is anodized using a hard anodizing condition of anodizing at 79-81V for 29-31 seconds, and the third anodization of step 4 is 29-31V. It may be anodizing treatment using a soft anodizing condition of anodizing for 29-31 minutes at this time, and at this time, ultra-superhydrophilicity is further improved to further improve dyeing uniformity and color clarity, and the above step 2
  • the secondary anodization of is anodized using hard anodizing conditions of anodizing at 80 V for 30 seconds, and the third anodizing of step 4 is performed using soft anodizing conditions of anodizing at 30 V for 30 minutes. It is particularly preferable to perform anodization treatment (see Experimental Examples 1 to 2).
  • the pore expansion in step 3 may be immersed for 25-35 minutes.
  • a hierarchical structure capable of exhibiting excellent superhydrophilicity is formed on the surface of the aluminum alloy, so that dyeing uniformity and color clarity are excellent.
  • a hierarchical structure capable of showing hydrophilicity is not formed (see Experimental Examples 1 to 2).
  • the pore expansion of step 3 may be immersion for 28-32 minutes.
  • a hierarchical structure capable of showing ultra-superhydrophilicity is formed on the surface of the aluminum alloy, thereby further improving dyeing uniformity and color clarity. When out of the above condition range, ultra superhydrophilicity may not appear (see Experimental Examples 1 to 2).
  • the pore expansion of step 3 may be immersed for 29-31 minutes, at this time, the ultra-superhydrophilicity is further improved, so that the dyeing uniformity and color clarity are further improved, and the immersion for 30 minutes It is particularly preferable (see Experimental Examples 1 to 2).
  • the secondary anodization of step 2 and the third anodization of step 4 are hard anodes each anodizing at 75-85V for 25-35 seconds. It may be anodizing treatment using hard anodizing conditions. When performing anodization under the above conditions, there is an effect of forming a clear pillar-on-pore structure on the surface of the aluminum alloy, and outside the above condition range, no pillar-on-pore structure is formed (see Experimental Example 1). ).
  • the second anodization of step 2 and the third anodization of step 4 are anodized using a hard anodizing condition of anodizing at 78-82V for 28-32 seconds, respectively. It can be.
  • a hard anodizing condition of anodizing at 78-82V for 28-32 seconds can be.
  • the pore expansion in step 3 may be immersed for 55-65 minutes.
  • a clear pillar-on-pore structure is formed on the surface of the aluminum alloy (see Experimental Example 1).
  • the pore expansion of step 3 may be immersion for 58-62 minutes.
  • the pores are expanded under the above conditions, a clearer pillar-on-pore structure is formed on the surface of the aluminum alloy (see Experimental Example 1).
  • the electrolyte in which the first anodization in step 1, the second anodization in step 2, and the third anodization in step 3 is performed is sulfuric acid (H 2 SO).
  • phosphoric acid H 3 PO 4
  • oxalic acid C 2 H2O 4
  • chromic acid hydrofluoric acid
  • potassium hydrogen phosphate K 2 HPO 4
  • a material on which the metal to be anodized is formed is used as a working electrode in the oxidation treatment tank containing the electrolyte, and then an anode is attached to it, and then platinum (Pt) or carbon ( carbon) electrode as a counter electrode, and may be oxidized by attaching a cathode.
  • the electrolytic solution may be made at a temperature of -5 to 10°C using 0.1-0.5M oxalic acid as an electrolytic solution, and more preferably made at a temperature of -2 to 2°C and a 0.2-0.4M oxalic acid electrolyte. have.
  • the dye of step 5 may be an organic dye or an inorganic dye, for example, "Anodizing and Coloring of Aluminum Alloys" by S.Kawai ASM International (2002) It may be a dye disclosed in, and includes acid dyes, acid metal complex dyes, acid mediated dyes, direct dyes, weak acid dyes, disperse dyes, dissolution reducing dyes, active dyes, alkaline dyes, dyes soluble in alcohol and inorganic metal salt It may be one or more selected from those consisting of dyes to contain.
  • a hydrophilic (water-soluble) dye may be used, and examples of the hydrophilic dye include TAC dye (TAC ORANGE LH (301), TAC BLACK BLH (411), TAC BLUE BRL (507), TAC) manufactured by OKUNO, Japan.
  • TAC dye TAC ORANGE LH (301), TAC BLACK BLH (411), TAC BLUE BRL (507), TAC
  • PINK GLH (139), TAC YELLOW RHM (201), etc.), dyes of CLARIANT headquartered in Switzerland (ODYE YELLOW 3GL, ODURE ORANGE RL, ODYE BLUE 2LW, ODAL BLACK GL, ODAL GREEN 3LW, etc.), HANAMI of Japan Dyes (ALUMINARL YELLOW-W, ALUMINARL ORANGE-W, ALUMINARL RED-W, ALUMINARL BLUE-W, ALUMINARL BLACK-W, etc.) and Japanese ORIENT's dyes (YELLOW MF-101G, ORANGE SW-5201, RED MF-301B, BLUE SW-5602, BLACK SW-5802, etc.) can be used, but is not limited thereto.
  • the dyeing of step 5 is any selected from the group consisting of spray coating, vapor coating, curtain coating, inkjet coating, screen printing, bar coating, slit die coating, and dip coating. It can be done in one way.
  • the method of dyeing the surface of an aluminum alloy according to the present invention may further include sealing an anodized film of the aluminum alloy dyed after step 5 above.
  • the sealing is also referred to as sealing, and may be coated with a clear coating agent in order to prevent dye fading on the surface of the anodized film and improve scratch resistance and durability.
  • the clear coating agent used for the sealing is not particularly limited as long as it is a clear coating agent (sealing agent) applicable to coating on a metal, metal oxide, or metal hydroxide. More specifically, it may be one or more selected from the group consisting of a matte clear coating agent, a glossy/matte clear coating agent, a clear ceramic coating agent, and a glass coating agent.
  • the sealing includes hydration sealing, which is a sealing method using pressurized steam, metal salt sealing, which is a sealing method using hot water including metal salt, organic material sealing, which is a method of applying or immersing organic substances such as oil, and coating the surface of an anodized film. It may be performed by any one method selected from the group consisting of sealing by phosphorus coating, electrolytic sealing, immersion sealing, and low-temperature sealing using a low-temperature sealing agent.
  • metal salt complex salts such as nickel, cobalt, cadmium, zinc, copper, aluminum, and lead, nitrate, sulfate, etc. may be used, and Dia Cold #500 may be used as the low-temperature sealing agent.
  • Sealing by spray gun, electrostatic coating, may be sealing treatment by electrodeposition coating.
  • the aluminum alloy on which the anodized film is formed is sealed using an immersion sealing method in which nickel acetate (nickel acetate) is impregnated.
  • the method of dyeing the surface of an aluminum alloy according to the present invention implements superhydrophilicity by controlling the anodization film shape of the aluminum alloy surface in a hierarchical structure by performing anodization and pore expansion processes under specific conditions. As the coloring of the hydrophilic dye becomes easier, the dyeing time is also shortened, the color realization is excellent, and the dyeing is uniform and clear (see Experimental Examples 1 to 2).
  • the aluminum alloy that can be used in the present invention is preferably a 5000 series aluminum alloy such as Al-Mg series.
  • the 5000 series aluminum alloys are Al 5005, Al 5023, Al 5042, Al 5052, Al 5054, Al 5056, Al 5082, Al 5083, Al 5084, Al 5086, Al 5154, Al 5182, Al 5252, Al 5352, Al 5383 , Al 5454, Al 5456, Al 5457, Al 5657 and Al 5754 may be one or more selected from the group consisting of.
  • the present invention provides an aluminum alloy dyed by the aluminum alloy dyeing method.
  • the aluminum alloy according to the present invention may have a three-dimensional anodic aluminum oxide layer formed on its surface.
  • an anodized film having a hierarchical structure may be formed.
  • the upper layer is a Big pore size layer formed through HA-PW treatment (corresponding to Steps 1 to 3)
  • the lower layer is a Small pore size layer formed through MA treatment (corresponding to Step 4).
  • the HA-PW-treated layer (Big pore size) becomes the upper layer
  • the MA-treated layer (Small pore size) becomes the lower layer.
  • the aluminum alloy having the layered anodized film according to the exemplary embodiment of the present invention has superhydrophilicity/ultra superhydrophilicity, and the introduction of a hydrophilic dye therein has the effect of remarkably improving the coloring efficiency of the dye.
  • the hydrophilic dye is colored in a form enclosed in the pores formed on the upper and lower layers of the anodized film, the degree of hydrophilicity of the anodized film is important.
  • the dye may be supported on the pores having a pillar-on-pore structure and at the same time, the dye may be supported in the space between the pillars and the pillars formed on the pores. Accordingly, an effect of uniform and clear dyeing of the aluminum alloy may be exhibited.
  • Al 5052 pore widening
  • VW voltage modulation
  • Component information of the aluminum 5052 alloy is as follows; Mg 2.2 ⁇ 2.8%, Si 0.25%, Fe 0.40%, Cu 0.10%, Mn 0.10%, Zn 1.0%, Cr 0.15 ⁇ 0.35% and Al Balance.
  • Step 1 Pre-patterning process through primary anodization and chemical etching
  • the electrolytically polished aluminum 5052 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 the 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.
  • 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 Second and third anodization and pore expansion process
  • the second and third anodization processes of the embodiment were performed under the same acid electrolyte conditions as the first anodization process of step 1, and soft anodization (MA) or 80V using a relatively low voltage of 40V.
  • soft anodization MA or 80V using a relatively low voltage of 40V.
  • HA hard anodization
  • anodization was performed by selectively controlling the magnitude and sequence of voltages applied during the secondary and tertiary anodization.
  • the soft anodization was performed at 40V for 30 minutes
  • the hard anodization was performed at 80V for 30 seconds.
  • 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 30 to 60 minutes before performing the third anodization, and then, Third anodization was performed to grow an aluminum anodized film.
  • PW pore widening
  • step 1 Perform MA ⁇ PW ⁇ MA 40 30 30 40 30
  • step 2 Perform MA ⁇ PW ⁇ HA 40 30 80 0.5
  • Example 3 Perform HA ⁇ PW ⁇ MA 80 0.5
  • Example 4 Perform HA ⁇ PW ⁇ HA 80 0.5 30 80 0.5
  • Example 5 Perform MA ⁇ PW ⁇ MA 40 30 40 30
  • Example 6 Perform MA ⁇ PW ⁇ HA 40 30 40 80 0.5
  • Example 7 Perform HA ⁇ PW ⁇ MA 80 0.5 40 40 30
  • Example 8 Perform HA ⁇ PW ⁇ HA 80 0.5 40 80 0.5
  • Example 9 Perform MA ⁇ PW ⁇ MA 40 30 50 40 30
  • Example 10 Perform MA ⁇ PW ⁇ HA 40 30 50 80 0.5
  • Example 11 Perform HA ⁇ PW ⁇ MA 80 0.5 50 40 30
  • Example 12 Perform HA ⁇ PW ⁇ HA 80 0.5 50 80 0.5
  • Example 11 Perform HA ⁇ PW ⁇ MA 80 0.5 50 80 0.5
  • Example 12 Perform HA ⁇ PW ⁇ HA 80 0.5 50 80 0.5
  • Example 11 Perform HA ⁇ PW ⁇ MA 80
  • the obtained aluminum alloy anodized film was observed for its surface and cross-sectional shape through the method of Experimental Example 1 below.
  • Each of the aluminum alloy anodized films of Examples 1 to 16 and Comparative Examples 1 to 4 was dyed with a dye, followed by sealing and drying to perform dyeing.
  • the aluminum alloy anodized coatings of Examples 1 to 16 and Comparative Examples 1 to 4 were prepared by using TAC ORANGE-LH (301), an anodized aluminum alloy color dye made by OKUNO in Japan, in pure water 1 to 5 g/ Dyeing (coloring) was performed by immersing in a solution dissolved at a concentration of L for 30 seconds to 15 minutes.
  • each of the dyed aluminum alloy anodized films was immersed in a nickel acetate solution having a concentration of 7 g/L and a temperature of 65 to 85° C. for 5 to 30 minutes to form a sealing layer, followed by sealing treatment (sealing treatment). Subsequently, the sealed aluminum alloy anodized film was dried at 70 to 80° C. for about 10 to 30 minutes.
  • Example 1 Structural characteristics analysis of an aluminum alloy anodized film according to secondary and tertiary anodic oxidation conditions (voltage and time) and pore expansion time
  • 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 structure of the aluminum alloy anodized film, as shown in FIGS. 2 to 5.
  • 2 to 5 are top views and cross-sections of an aluminum alloy anodized film formed on the prepatterned aluminum alloy surfaces of Examples 1 to 4, 5 to 8, 9 to 12 and 13 to 16 according to the present invention, respectively.
  • This is a scanning electron microscope (SEM) image of a three-dimensional structure in (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 to 60 minutes, and scale bars of the surface and cross-section were 200 nm and 1 ⁇ m, respectively.
  • SEM scanning electron microscope
  • the result was that the diameter of the pores in the secondary anodization region of the aluminum alloy anodization film was increased by the PW process, 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 of Examples 1 to 16, the criteria for the secondary and tertiary anodization regions can be classified by the size transition of the pores.
  • 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 magnitude of the anodization voltage can affect the size of the pores.
  • Example 3 prepared by performing PW in the HA ⁇ PW ⁇ MA mode for 30 minutes, 3 of the lower part (inside close to the aluminum alloy surface) in the cross-view image.
  • Anodic oxide having a structure in which linear pores are formed in the secondary anodization region, and linear pores having a larger diameter than the pores in the tertiary anodization region are formed in the secondary anodization region formed on the third anodization region. It was found that was formed, and it was confirmed that an anodized film in the form of a hierarchical structure was prepared.
  • the average pore diameter (D P ) of the secondary anodization region of Example 3 was 100 nm
  • the interpore distance (D int ) was 136 nm
  • the third anodization region was It was confirmed that the average D P was 24 nm
  • the average D int was 99 nm.
  • the pores that appear in dark black are the pores in the secondary anodization area
  • the pores that appear in light black are the pores in the third anodization area
  • the pores that appear in black are white (bright It was confirmed that the portion in which the anode oxide of (gray) is formed is a tip-like structure portion formed in the secondary anodization region.
  • Example 12 unlike other examples in which linear pores are formed, an anodized film having a pillar-on-pore shape in which pillars are formed on the pore structure was prepared. Confirmed. In particular, it was confirmed that a much clearer pillar-on-pore shape was exhibited when prepared under the conditions of Example 16.
  • the magnitude of the secondary and tertiary anodization voltage which is a parameter, directly affects the size of the pores, controlling the pore diameter and the gap between pores and pores, as well as the growth of a three-dimensional aluminum anodized film.
  • the condition of HA (80V, 30sec) ⁇ PW (60min) ⁇ HA (80V, 30sec) of Example 16 was the condition for producing the most clear anodized layer of POP structure. It was confirmed that the conditions of HA (80V, 30sec) ⁇ PW(30min) ⁇ MA(40V, 30min) of Example 3 were conditions capable of producing a hierarchical anodized film.
  • 6 to 8 are each measuring the contact angle of the water droplets of the aluminum alloy anodized film formed on the pre-patterned aluminum alloy surface of Examples 1 to 4, Examples 13 to 16 and Comparative Examples 5 to 8 according to the present invention. This is an image showing the result.
  • the porous aluminum alloy anodizing films of Examples 1 to 4, 13 to 16 and Comparative Examples 5 to 8 prepared by performing the anodization process were an aluminum alloy base material that was not subjected to anodization ( It was confirmed that the wettability to water is higher than that of control).

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Abstract

La présente invention concerne un procédé de coloration d'un alliage d'aluminium afin de mettre en œuvre une couleur uniforme et vive. Le procédé de coloration d'un alliage d'aluminium, commande, selon la présente invention, par le biais de la commande d'une condition d'anodisation et d'un temps d'élargissement de pores, la forme de pore, le diamètre et la densité d'une couche d'aluminium anodisée qui doit être formée sur la surface d'un alliage d'aluminium, de manière à mettre en œuvre une structure hiérarchique superhydrophile, ce qui facilite la coloration d'un colorant hydrophile et réduit le temps de coloration et, étant donné que l'uniformité de teinture, la netteté de la couleur et la durabilité sont excellentes, la présente invention peut être utilisée dans divers domaines industriels nécessitant la mise en œuvre d'une couleur externe, tels que celui d'un boîtier de dispositif électronique, des couvercles d'éclairage tels que des DEL, des échangeurs de chaleur, des tuyaux, des structures routières, des automobiles, des avions, des navires et des générateurs d'énergie.
PCT/KR2020/015809 2019-11-14 2020-11-13 Procédé d'amélioration de la mise en œuvre d'une couleur vive sur une surface superhydrophile d'alliage d'aluminium WO2021096226A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006328467A (ja) * 2005-05-25 2006-12-07 Al Green Kk 陽極酸化皮膜付きアルミ基材及びその製造方法
KR20140094678A (ko) * 2013-01-11 2014-07-31 지케이 주식회사 알루미늄 합금의 표면처리방법 및 패턴을 갖는 전자제품용 알루미늄 합금 커버
KR20150092948A (ko) * 2014-02-06 2015-08-17 인 경 황 알루미늄 다이캐스팅 소재의 표면처리방법
CN107059088A (zh) * 2017-03-29 2017-08-18 深圳天珑无线科技有限公司 壳体及其制备方法、电子装置
US20180016696A1 (en) * 2016-07-15 2018-01-18 National Cheng Kung University Method for dye-free coloring of one-time anodic aluminum oxide surface

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101451425B1 (ko) * 2007-10-08 2014-10-21 고려대학교 산학협력단 알루미늄 소재의 자가세정능 부여를 위한 표면 개질 방법
KR20090131117A (ko) 2008-06-17 2009-12-28 한국생산기술연구원 천연식물을 이용한 알루미늄의 염색처리 방법
TWI498431B (zh) * 2009-09-11 2015-09-01 Nippon Light Metal Co 壓模用鋁模座用素材、壓模用鋁模座及壓模
KR20110074269A (ko) * 2009-12-24 2011-06-30 고려대학교 산학협력단 물방울의 표면부착 특성 조절이 가능한 알루미늄의 표면 처리방법
KR20130134826A (ko) * 2012-05-31 2013-12-10 고려대학교 산학협력단 정밀 액적 디스펜서용 자기 세정가능 초소수성 팁의 제조방법 및 그 방법에 의해 제조된 팁
KR102130665B1 (ko) * 2015-09-16 2020-07-06 한국전기연구원 초발수용 몰드 제조방법, 초발수용 몰드를 이용한 초발수용 재료 및 그 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006328467A (ja) * 2005-05-25 2006-12-07 Al Green Kk 陽極酸化皮膜付きアルミ基材及びその製造方法
KR20140094678A (ko) * 2013-01-11 2014-07-31 지케이 주식회사 알루미늄 합금의 표면처리방법 및 패턴을 갖는 전자제품용 알루미늄 합금 커버
KR20150092948A (ko) * 2014-02-06 2015-08-17 인 경 황 알루미늄 다이캐스팅 소재의 표면처리방법
US20180016696A1 (en) * 2016-07-15 2018-01-18 National Cheng Kung University Method for dye-free coloring of one-time anodic aluminum oxide surface
CN107059088A (zh) * 2017-03-29 2017-08-18 深圳天珑无线科技有限公司 壳体及其制备方法、电子装置

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