WO2022108011A1 - Procédé d'anodisation blanche utilisant des nanoparticules - Google Patents

Procédé d'anodisation blanche utilisant des nanoparticules Download PDF

Info

Publication number
WO2022108011A1
WO2022108011A1 PCT/KR2021/005256 KR2021005256W WO2022108011A1 WO 2022108011 A1 WO2022108011 A1 WO 2022108011A1 KR 2021005256 W KR2021005256 W KR 2021005256W WO 2022108011 A1 WO2022108011 A1 WO 2022108011A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
solution
white
nanoparticles
aluminum material
Prior art date
Application number
PCT/KR2021/005256
Other languages
English (en)
Korean (ko)
Inventor
이은한
문성모
권두영
한영기
Original Assignee
주식회사 엔더블유
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 엔더블유 filed Critical 주식회사 엔더블유
Publication of WO2022108011A1 publication Critical patent/WO2022108011A1/fr

Links

Images

Classifications

    • 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
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/12—Anodising more than once, e.g. in different baths

Definitions

  • the present invention provides a white anodizing method in which white is realized by impregnating the pores of the film with nanoparticles using a process of anodizing including a 2-step film treatment and a pore-widening process and dispersion-treated nanoparticles, and It's about white aluminum.
  • the white anodizing technology for aluminum alloys (hereinafter referred to as aluminum) is impossible to color with white dyes by anodizing such as the sulfuric acid method of current industrial aluminum due to the size of the white dye molecules.
  • the existing white pigment is nano-processed to an appropriate level through a nano facility, and it is effectively dispersed and used as a whitening colorant.
  • An object of the present invention is to provide a white anodizing method using a nanoparticle solution of a white pigment, an electrolyte change in a film tank, and a 2-step anodizing process and a pore widening process in order to secure aluminum processed by white anodizing.
  • the white anodizing method comprises the steps of: (a) immersing an aluminum material in a first acid solution to form a primary film on the surface of the aluminum material; (b) removing the coating; (c) immersing the aluminum from which the film has been removed in the first acid solution to form a secondary film on the surface of the aluminum material; (d) immersing the aluminum material on which the film is formed in a second acid solution; and (e) immersing the immersed aluminum material in a nanoparticle solution, wherein the nanoparticle solution includes inorganic nanoparticles having a particle diameter of 1 to 30 nm.
  • White aluminum according to the present invention is an aluminum material; a film disposed on the surface of the aluminum material; pores formed in the film; and nanoparticles disposed in the pores.
  • the white anodizing method according to the present invention is an effect that white is realized by impregnating the pores formed in the oxide film with nanoparticles through the two-step anodizing treatment, pore widening, and impregnation treatment with a solution mixed with nanoparticles and dispersing agent there is
  • the nanoparticles are impregnated into the pores of the oxide film and the specular reflection of light is increased, the surface of the oxide film is brightened and the brightness value (L*) is increased, so that white is realized.
  • aluminum manufactured according to the white anodizing method can realize white color conforming to Korean industrial standards while exhibiting physical properties equal to or higher than the existing corrosion resistance, wear resistance, and hardness.
  • 1 is a solution in which nanoparticles of the present invention are dispersed.
  • FIG. 2 is a surface photograph of a whitening-treated specimen with an anodizing film formed by treating the dispersion solution of FIG. 1 at a current density of 77 mA/cm 2 in a 3wt% oxalic acid solution at 0° C. for 10 minutes.
  • 5 is a graph showing the change in the thickness of the film according to the magnitude of the applied voltage.
  • FIG. 7 is a photograph of the surface of Al6061 alloy subjected to anodization in a 3wt% oxalic acid solution at 10°C for 10 minutes by applying a voltage in the range of 80 to 120V.
  • 9 is a surface image of a specimen obtained by applying 100 V in a 3 wt% oxalic acid solution at 10° C. and processing for 60 minutes to obtain an anodized film formed by varying the pore widening treatment time in a 0.1 M phosphoric acid solution.
  • Figure 10 is a whitening in a solution in which nanoparticles of various sizes are dispersed by applying 100V in a 3wt% oxalic acid solution at 10°C and pore widening for 60 minutes in a 0.1 M phosphoric acid solution to an anodized film formed by treatment for 60 minutes This is a photograph of the surface of the treated specimen.
  • 11 is It is a photograph of a specimen obtained in the process of 2-step anodizing treatment by applying 80V in a 3wt% oxalic acid solution at 10°C.
  • 17 is an EDS component analysis result of the particles adsorbed to the surface observed in FIG. 14
  • FIG. 20 is a 3wt% oxalic acid solution at 10°C using the solutions (a), (b), (c) and (f) shown in FIG. 18, respectively.
  • This is a photo of a specimen that was whitened in the film formed by applying 90V to the ionizer and performing 2-step anodizing for 30 minutes.
  • 21 shows the average particle size Four nanopowders of 20 nm or less ((a) Al 2 O 3 , (b) TiO 2 , (c) ZnO, (d) Ag powder) is added to distilled water to which SDS has been added, and is a solution prepared through high-power ultrasonic dispersion treatment for 1 hour.
  • FIG. 22 is a photograph of a specimen subjected to whitening treatment on an anodized film formed by 2-step anodizing for 30 minutes by applying 90 V in a 3 wt% oxalic acid solution at 10° C. using the dispersion solution shown in FIG. 21 .
  • FIG. 25 is a photograph showing the change of the surface of the coating film by vacuum impregnation in a solution (FIG. 21) in which nanoparticles of various sizes are dispersed by pore widening of the anodized film formed in a sulfuric acid solution for 10 minutes.
  • 26 shows two types of whitening solutions (product names: AT101, AT102), and the average particle size is It is a solution in which binary alloy particles of 20 nm or less are dispersed.
  • FIG. 27 is It is a photograph of a specimen treated with different whitening conditions in the whitening solution shown in FIG. 26 on the anodizing film formed in a 3wt% oxalic acid solution at 10°C.
  • an arbitrary component is disposed on the "upper (or lower)" of a component or “upper (or below)” of a component means that any component is disposed in contact with the upper surface (or lower surface) of the component. Furthermore, it may mean that other components may be interposed between the component and any component disposed on (or under) the component.
  • each component when it is described that a component is “connected”, “coupled” or “connected” to another component, the components may be directly connected or connected to each other, but other components are “interposed” between each component. It should be understood that “or, each component may be “connected,” “coupled,” or “connected,” through another component.
  • Anodizing is when an aluminum part is energized in an electrolyte solution as an anode, the aluminum surface is oxidized by oxygen generated at the anode, and a film of aluminum oxide (Al 2 O 3 ) is formed. During anodizing, if an appropriate voltage is applied, a 1 micrometer ( ⁇ m) oxide film grows in about 1 minute.
  • the film described in the present invention refers to an oxide film.
  • the two-step method in order to align and enlarge the pores of the surface to be anodized, the two-step method was used for coating twice, and a pore widening process was performed.
  • the anodized surface of aluminum is coated with a solution such as chromic acid. peeled off.
  • the white anodizing method using nanoparticles of the present invention comprises the steps of (a) immersing an aluminum material in a first acid solution to form a first film on the surface of the aluminum material, (b) removing the film, (c) ) immersing the aluminum from which the film has been removed in the first acid solution to form a secondary film on the surface of the aluminum material, (d) immersing the aluminum material on which the film is formed in a second acid solution; and (e) immersing the immersed aluminum material in a nanoparticle solution.
  • the nanoparticle solution has a feature that includes inorganic nanoparticles having a particle diameter of 1 to 30 nm.
  • the inorganic nanoparticles preferably include at least one of Al 2 O 3 , TiO 2 , ZnO, and Ag. And it is more preferable to include TiO 2 and ZnO having a refractive index of 2.0 or more.
  • the nanoparticle solution is formed by mixing inorganic nanoparticles, a dispersing agent, and distilled water, and then performing ultrasonic dispersion treatment at a frequency of 10 kHz or higher.
  • the nanoparticle solution is preferably mixed with 30-50 g of nanoparticles per 1 liter (L) of distilled water, and 40-60 g of a dispersant is preferably mixed.
  • the dispersant may include one or more of anionic dispersants, cationic dispersants, and nonionic dispersants.
  • the anionic dispersant may include at least one of sodium dodecyl sulfate (SDS), lithium dodecyl sulfate (LDS), sodium dodecylbenzene sulfonate (NaDDS), sodium dodecyl sulfonate (SDSA), and sodium dodecylbenzenesulfonate (SDBS), which are alkyl sulfates. have.
  • SDS sodium dodecyl sulfate
  • LDS lithium dodecyl sulfate
  • NaDDS sodium dodecylbenzene sulfonate
  • SDSA sodium dodecyl sulfonate
  • SDBS sodium dodecylbenzenesulfonate
  • the cationic dispersant may include at least one of cetyltrimethyl ammonium chloride (CTAC), cetyltrimethyl ammonium bromide (CTAB), and dodecyl-trimethyl ammonium bromide (DTAB).
  • CTAC cetyltrimethyl ammonium chloride
  • CTAB cetyltrimethyl ammonium bromide
  • DTAB dodecyl-trimethyl ammonium bromide
  • Nonionic dispersants include glycerol monostearate, sorbitan monooleate, Tween 80, PVA (Polyvinyl alcohol), PMA (Polymethyl acrylate), MC (Methyl cellulose), CMC (Carboxyl methyl cellulose), GA (Gum Arabic), Polysaccharide (Dextrin), PEI (Polyethylenimine), PVP (Polyvinylpyrrolidone), PEO (Polyethylene oxide), Poly(ethylene oxide)-Poly(butylene oxide) may include at least one terpolymer.
  • PVA Polyvinyl alcohol
  • PMA Polymethyl acrylate
  • MC Metal cellulose
  • CMC Carboxyl methyl cellulose
  • GA Ga Arabic
  • PEI Polyethylenimine
  • PVP Polyvinylpyrrolidone
  • PEO Polyethylene oxide
  • Poly(ethylene oxide)-Poly(butylene oxide) may include at least one
  • the dispersant may include sodium dodecyl sulfate (SDS).
  • SDS sodium dodecyl sulfate
  • the nanoparticle solution is formed by dispersing treatment with high-power ultrasonic waves using a frequency of 10 to 30 kHz, adjusting the amplitude at 10 to 90%, and dispersing for 30 minutes or more.
  • micrometer inorganic beads are nano-treated to a size of 10 to 30 nm with a medium of a stirring mill and used as a white pigment.
  • micrometer inorganic beads are used as the medium of the high-speed medium stirring mill, finer pulverization, dispersion, and mixing are possible compared to those using the conventional medium. And since the purity of the obtained fine powder and the generation of impurities due to abrasion of the medium are extremely small, it is possible to obtain an excellent result of controlling the decrease in the purity of the product powder after milling to an extremely low level compared to the raw material powder before milling.
  • the inorganic bead has an extremely sharp particle size distribution.
  • the particle size of the powder which is a product of the mill, becomes sharp, and the quality of the powder becomes homogeneous.
  • Nano-manufacturing equipment pulverizes micro-sized materials into nanoparticles of a certain size by mechanical multi-step impact, collects them, cools them, and then applies strong physical multi-step impacts to convert them into fine nanoparticles.
  • the nano-manufacturing equipment includes a crushing unit, a collecting unit, a pre-processing unit, an impact unit, and a sorting unit.
  • the pulverizing unit is to automatically sort each by a certain size.
  • the pulverizing unit mechanically pulverizes the introduced nanoparticle raw material in multiple steps sequentially and pulverizes it into nano-sized nanoparticles.
  • the pretreatment unit cools the nanoparticles introduced from the collecting unit and mixes them with an inert gas for pretreatment.
  • the impact unit is converted into fine nanoparticles by sequentially applying multi-step physical shocks to the nanoparticles that have been pretreated from the pretreatment unit.
  • the sorting unit collects and concentrates the fine nanoparticles flowing in from the impact unit, and classifies them in multiple stages by size.
  • the aluminum material is immersed in a first acid solution containing an oxalic acid or/and sulfuric acid solution, and then a voltage is applied to form a primary film on the surface of the aluminum material.
  • Oxalic acid may be 1-20 wt%, and sulfuric acid may be 1-40 wt%.
  • oxalic acid may be 0 ⁇ 30 °C.
  • step (b) the coating is removed by immersion in a mixed solution of chromic acid or/and phosphoric acid.
  • Chromic acid may be 1-30 wt%, and phosphoric acid may be 1-30 wt%.
  • the chromic acid may be 20 ⁇ 70 °C.
  • the aluminum from which the film has been removed is immersed in the first acid solution again to form a secondary film on the surface of the aluminum material.
  • the aluminum material that has undergone two film formations has a film close to the thickness of one layer on the surface of the material because the primary film is removed.
  • step (d) the aluminum material on which the film is formed is immersed in a second acid solution containing a phosphoric acid solution. 0.01 ⁇ 1M phosphoric acid solution at 10 ⁇ 50°C can be used.
  • the step of immersing in the second acid solution increases the porosity and pore size formed in the film, so that the nanoparticles can be sufficiently introduced into the pores.
  • the porosity and pore size formed in the film after immersion in the second acid solution are greater than the porosity and pore size formed in the film before immersion in the second acid solution.
  • the porosity and the pore size formed in the coating film before immersion it is desirable to increase it by up to 50%.
  • the pore widening process was performed by immersion in the phosphoric acid solution for 10 to 60 minutes.
  • the color of the film formed through the 2-step anodizing treatment showed a brighter yellow color than the film formed through the 1-step anodizing treatment.
  • a two-step anodizing process is performed to form an oxide film with aligned pores.
  • the more well-ordered pores the easier it is to impregnate the nanoparticles, so that a larger amount of nanoparticles can be impregnated. This is considered to be a brighter color due to increased specular reflection of light as the pores are aligned by the 2-step anodizing treatment.
  • a vacuum impregnation method was used for the whitening treatment of the film.
  • Vacuum impregnation was performed by immersing the anodized specimen in a nanoparticle solution, maintaining a vacuum degree of 0.1 Mpa or less in a vacuum chamber, and processing for 5 minutes to 1 hour.
  • the color of the surface of the film tends to become brighter only when a nanoparticle solution dispersed using a dispersant and high-power ultrasonic wave is used, and the formed film is immersed in a phosphoric acid solution and then impregnated with ultrasonic waves, etc.
  • the anodized white aluminum includes an aluminum material, a film disposed on the surface of the aluminum material, pores formed in the film, and nanoparticles disposed in the pores.
  • nanoparticles show a state impregnated in the pores, and exhibit excellent white color due to this structure.
  • the inorganic nanoparticles preferably include at least one of Al 2 O 3 , TiO 2 , ZnO, and Ag.
  • the consumer demands the thickness of the surface (important in corrosion resistance), surface roughness, color, and the like, and in the case of parts, the hardness of the surface is also required.
  • the surface of the anodized aluminum is ceramic (Al 2 O 3 , aluminum oxide) and has a mirror surface.
  • the surface of anodized aluminum is evaluated as roughness according to the degree of roughness.
  • the thickness of the oxide film usually grows at a rate of about 1 ⁇ m per minute.
  • White and white referred to in the present invention are achromatic colors (black, gray, white) without any color, and reflect all light.
  • Achromatic colors are classified by the three elements of color, without hue and saturation, and by the height of the brightness. On the value (V) axis, the number increases from 0 to 10, where 0 means absolute black and 10 means absolute white. Black and white do not exist as object colors, and values ranging from 1.5 to 9.5 are usually used.
  • KS A0011 Color name of object color
  • white white
  • N1, N2, N3 ... are sometimes denoted by taking the first letter of neutral in English called achromatic color. If you look at the reflectance value (%) of brightness and 11 levels of achromatic color, black is N1.5 ⁇ N2, gray is N3 ⁇ N8, and white and white are N9 ⁇ N9.5.
  • the value of Y is the measured value of the luminous reflectance (%) of the brightness
  • the solution is shown in FIG. 1, and it was confirmed as a solution in which nanoparticles of different sizes were dispersed.
  • the pH of the solution was (a), 2.12 (b), 1.92 (c) ⁇ (f), 6.9 ⁇ 7.4, (a), (b) was acidic, (c) ⁇ (f) was neutral .
  • Nanoparticles have an average particle size Al 2 O 3 , TiO 2 , ZnO, and Ag of 20 nm or less are nanoparticles with different compositions and sizes.
  • Six solutions were mixed with the dispersant SDS and dispersed with high-power ultrasonic waves, and were used for whitening treatment.
  • FIG. 2 is a surface photograph of a whitening-treated specimen with an anodizing film formed by treating the dispersion solution of FIG. 1 at a current density of 77 mA/cm 2 in a 3wt% oxalic acid solution at 0° C. for 10 minutes.
  • the whitening treatment was performed for 10 minutes by immersing the anodizing film in the dispersion solution. After sonicating for 5 minutes in an ultrasonic device, vacuum impregnation was performed for 5 minutes in a vacuum chamber.
  • the initial rapid increase in voltage is due to the formation of a barrier-type oxide film on the surface of the aluminum at the initial stage of film formation, thereby increasing the resistance.
  • the voltage increased rapidly to 100V, then decreased by about 1 ⁇ 2V, and then the voltage showed a tendency to increase again. After that, the increase rate of the voltage showed a tendency to gradually slow down.
  • FIG. 4 is a photograph of the surface of Al6061 alloy subjected to anodization treatment for 10 minutes under a forming voltage in the range of 60 to 140V.
  • the surface color of the film formed at 60V was pale yellow. And as the applied voltage increased, the color of the film surface changed to dark yellow.
  • the thickness of the film increased as the magnitude of the applied voltage increased.
  • the color of the film is related to the thickness of the film, and as the thickness of the film increases, the color of the film becomes darker.
  • the voltage change according to the processing time showed a result that the voltage increased rapidly and linearly at the beginning, and the increase rate of the voltage gradually decreased after 90V.
  • FIG. 7 is a photograph of the surface of Al6061 alloy subjected to anodization in a 3wt% oxalic acid solution at 10°C for 10 minutes by applying a voltage in the range of 80 to 120V.
  • the color of the film formed in a 3wt% oxalic acid solution at 10°C showed a darker yellow with less gloss than the color of the anodized film formed in a 3wt% oxalic acid solution at 0°C.
  • the surface roughness of the film increased. Due to this, the probability that light causes diffuse reflection on the surface of the film increases, which is thought to indicate a darker color.
  • 9 is a surface image of a specimen obtained by applying 100 V in a 3wt% oxalic acid solution at 10° C. and processing for 60 minutes to obtain an anodized film formed by varying the pore widening treatment time in a 0.1 M phosphoric acid solution.
  • the pore widening process was performed by immersing in a 0.1 M phosphoric acid solution at 30° C. for 10 to 60 minutes.
  • the color of the oxalic acid film gradually changed from yellow to light gray according to the pore widening treatment time. After 60 minutes of treatment, the color of the oxalic acid film was light gray.
  • the color change of the surface of the film is caused by the pore widening treatment to increase the size of the pores in the film, that is, the porosity, and decrease the surface roughness. Therefore, it is thought that this is because the film color appears to be a brighter color.
  • FIG. 10 shows an anodized film formed by applying 100 V in a 3wt% oxalic acid solution at 10° C. for 60 minutes and pore widening in a 0.1 M phosphoric acid solution for 60 minutes, in a solution in which nanoparticles of various sizes are dispersed. This is a photograph of the surface of the whitened specimen.
  • 11 is It is a photograph of a specimen obtained in the process of 2-step anodizing treatment by applying 80V in a 3wt% oxalic acid solution at 10°C.
  • the oxide film formed through 2-step anodizing exhibited a brighter color.
  • the left half of the specimen is the part that has not been whitened.
  • the right half is the whitened part.
  • 16 is a FE-SEM image of a film anodized for 60 minutes by applying 80V in a 3wt% oxalic acid solution at 10°C.
  • Anodized film formed by 2-step anodizing (2)
  • the film of (1) has an average particle size Anodized film whitened by vacuum impregnation in a solution in which ZnO of 20 nm or less is dispersed, (3) anodized film treated with pore widening in 0.1M phosphoric acid solution at 30°C for 60 minutes, (4) Average particle diameter of the film in (3) this It is an anodized film that is whitened by vacuum impregnation in a solution in which ZnO of 20 nm or less is dispersed.
  • 17 is an EDS component analysis result of the particles adsorbed to the surface observed in FIG. 14 .
  • the components of the particles were analyzed as O, Al and Zn. And after the whitening treatment, it was confirmed that the ZnO particles were adsorbed to the surface without being impregnated into the pores.
  • (a) is a solution in which nanoparticles are added to distilled water
  • (b) to (e) are solutions prepared by adding sodium dodecyl sulfate (SDS) as a dispersing agent at different ultrasonic dispersion times.
  • SDS sodium dodecyl sulfate
  • (b) is 10 minutes
  • (c) is 30 minutes
  • (d) is 1 hour
  • (e) is dispersed by ultrasonic waves for 2 hours.
  • (f) is a solution dispersed for 2 hours using a high-power ultrasonic device.
  • FIG. 20 is a 3wt% oxalic acid solution at 10°C using the solutions (a), (b), (c) and (f) shown in FIG. 18, respectively.
  • This is a photo of a specimen that was whitened in the film formed by applying 90V to the ionizer and performing 2-step anodizing for 30 minutes.
  • 21 shows the average particle size Four nanopowders of 20 nm or less ((a) Al 2 O 3 , (b) TiO 2 , (c) ZnO, (d) Ag powder) is added to distilled water to which SDS has been added, and is a solution prepared through high-power ultrasonic dispersion treatment for 1 hour.
  • FIG. 22 is a photograph of a specimen obtained by whitening the anodized film formed by 2-step anodizing for 30 minutes by applying 90V in a 3wt% oxalic acid solution at 10°C using the dispersion solution shown in FIG. 21 .
  • the anodized film was fabricated through 2-step anodizing.
  • the primary film was formed by treatment at a current density of 30 mA/cm 2 in a 20 wt% sulfuric acid solution at 15° C. for 10 minutes.
  • the formed primary anodized film was immersed in a solution of chromic acid and phosphoric acid to completely dissolve the primary film.
  • a second anodization film was formed under the same conditions as in the first anodization to prepare a specimen.
  • the pore widening was treated by immersing the specimen in a 0.1 M phosphoric acid solution at 50° C., and the surface change of the anodized film was observed by varying the treatment time.
  • the lower half of the specimen was the whitened portion, and no surface change was observed visually after the whitening treatment.
  • FIG. 25 is a photograph showing the change of the surface of the coating film by pore widening treatment for 10 minutes on the anodized film formed in a sulfuric acid solution, and vacuum impregnation in a solution in which nanoparticles of various sizes are dispersed ( FIG. 21 ).
  • 26 shows two types of whitening solutions (product names: AT101, AT102), and the average particle size is It is a solution in which binary alloy particles of 20 nm or less are dispersed.
  • FIG. 27 is It is a photograph of a specimen treated with different whitening conditions in the whitening solution shown in FIG. 26 on the anodizing film formed in a 3wt% oxalic acid solution at 10°C.
  • (a) is a 2-step oxalic acid film specimen without whitening treatment
  • (b) is a 2-step anodizing treatment and then pore widening in 0.1 M phosphoric acid solution at 30°C for 1 hour
  • (c) and (d) are Specimens in which the pore-widening-treated oxalic acid film was vacuum-impregnated in AT101, AT102 solution for 10 minutes
  • (e) and (f) were autoclaved and pressure-impregnated using AT101, AT102 solution for 1 hour. to be.
  • the specimen and the whitening solution were filled in an autoclave and then maintained in an oven at 180° C. for 1 hour.
  • the gray oxalic acid film treated with pore widening changed to a shiny light gray.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

La divulgation concerne un procédé d'anodisation blanche utilisant des nanoparticules, pour obtenir de l'aluminium blanc. Le procédé d'anodisation blanche selon la présente invention comprend les étapes consistant : (a) à immerger un matériau d'aluminium dans une première solution d'acide pour former de façon primaire un film sur la surface du matériau d'aluminium; (b) à retirer le film; (c) à immerger l'aluminium, dont on a retiré le film, pour former de façon secondaire un film sur la surface du matériau d'aluminium; (d) à immerger, dans une seconde solution d'acide, le matériau d'aluminium sur lequel est formé le film; (e) à immerger, dans une solution de nanoparticules, le matériau d'aluminium immergé; et (f) à maintenir le degré de vide du matériau d'aluminium immergé dans la solution de nanoparticules à 0,1 Mpa ou moins dans une chambre à vide, la solution de nanoparticules comprenant des nanoparticules inorganiques ayant un diamètre de particule de 1 à 30 nm. L'aluminium blanc selon la présente invention comprend : un matériau d'aluminium; un film disposé sur la surface du matériau d'aluminium; des pores formés dans le film; et des nanoparticules disposées dans les pores.
PCT/KR2021/005256 2020-11-19 2021-04-26 Procédé d'anodisation blanche utilisant des nanoparticules WO2022108011A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2020-0155112 2020-11-19
KR1020200155112A KR102244376B1 (ko) 2020-11-19 2020-11-19 나노입자를 이용한 화이트 아노다이징 방법

Publications (1)

Publication Number Publication Date
WO2022108011A1 true WO2022108011A1 (fr) 2022-05-27

Family

ID=75725595

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2021/005256 WO2022108011A1 (fr) 2020-11-19 2021-04-26 Procédé d'anodisation blanche utilisant des nanoparticules

Country Status (2)

Country Link
KR (1) KR102244376B1 (fr)
WO (1) WO2022108011A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06240493A (ja) * 1993-02-19 1994-08-30 Nippon Alum Co Ltd アルミニウム陽極酸化皮膜の塗装方法
JPH0762594A (ja) * 1993-08-27 1995-03-07 Dainichiseika Color & Chem Mfg Co Ltd 薄膜及びその製造方法並びにその薄膜を用いる機能素子
KR20070010321A (ko) * 2005-07-18 2007-01-24 성균관대학교산학협력단 기능화된 다공성 양극산화 알루미늄의 제조방법 및 그를이용한 광간섭 바이오센서의 제조방법 및 바이오센서
KR20070039199A (ko) * 2005-10-07 2007-04-11 월드엔앤씨 주식회사 알루미늄 소재의 표면처리방법 및 그 표면처리방법에 의해제조된 알루미늄 소재
KR20170076791A (ko) * 2012-06-22 2017-07-04 애플 인크. 백색으로 보이는 양극산화 필름 및 이를 형성하기 위한 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06240493A (ja) * 1993-02-19 1994-08-30 Nippon Alum Co Ltd アルミニウム陽極酸化皮膜の塗装方法
JPH0762594A (ja) * 1993-08-27 1995-03-07 Dainichiseika Color & Chem Mfg Co Ltd 薄膜及びその製造方法並びにその薄膜を用いる機能素子
KR20070010321A (ko) * 2005-07-18 2007-01-24 성균관대학교산학협력단 기능화된 다공성 양극산화 알루미늄의 제조방법 및 그를이용한 광간섭 바이오센서의 제조방법 및 바이오센서
KR20070039199A (ko) * 2005-10-07 2007-04-11 월드엔앤씨 주식회사 알루미늄 소재의 표면처리방법 및 그 표면처리방법에 의해제조된 알루미늄 소재
KR20170076791A (ko) * 2012-06-22 2017-07-04 애플 인크. 백색으로 보이는 양극산화 필름 및 이를 형성하기 위한 방법

Also Published As

Publication number Publication date
KR102244376B1 (ko) 2021-04-27

Similar Documents

Publication Publication Date Title
WO2013009133A2 (fr) Composition de résine pour un traitement de surface et tôle d'acier revêtue de celle-ci
WO2019107720A1 (fr) Pigment nacré à des fins de sécurité comprenant un matériau fluorescent organique ou inorganique
WO2021177551A1 (fr) Procédé d'amélioration de la stabilité à l'oxydation du mxène par le biais de la commande d'un groupe fonctionnel de surface
WO2014137192A2 (fr) Substrat transparent comprenant une ligne métallique fine et procédé de fabrication de celui-ci
WO2015099498A1 (fr) Matière de base à couleur traitée et procédé de traitement de couleur de matière de base pour cette dernière
WO2022108011A1 (fr) Procédé d'anodisation blanche utilisant des nanoparticules
WO2017217750A1 (fr) Composition en solution pour le traitement de surface d'une tôle d'acier, tôle d'acier plaquée à base de zinc traitée en surface avec ladite composition, et son procédé de fabrication
WO2019198929A1 (fr) Pâte conductrice à base de cuivre et son procédé de fabrication
WO2019132187A1 (fr) Particule de pigment inorganique d'oxyde de titane et son procédé de préparation
WO2019035503A1 (fr) Procédé de préparation de point quantique de graphène dopé à l'azote, point quantique de graphène dopé à l'azote et photopile comprenant un point quantique de graphène dopé à l'azote
WO2017018599A1 (fr) Poudre de carbure de silicium, corps fritté en carbure de silicium, suspension épaisse de carbure de silicium, et procédé de préparation
WO2020076138A1 (fr) Solution de revêtement complexe, structure de substrat métallique fabriquée à l'aide de celle-ci, et son procédé de fabrication
WO2017135619A1 (fr) Joint organique enrobé d'argent, son procédé de préparation, et composition de pâte d'argent utilisant un joint organique enrobé d'argent pour cellule solaire
WO2018221840A1 (fr) Procédé de préparation de pigment irisé pour la sécurité et la sureté revêtu de luminophore composite organique et inorganique
WO2021256906A1 (fr) Tôle d'acier plaqué présentant d'excellentes propriétés de résistance à la corrosion, d'aptitude au façonnage et de qualité de surface et son procédé de fabrication
WO2019225976A1 (fr) Particules de pigment présentant une isolation, une dispersibilité et une résistance améliorées
WO2023277541A1 (fr) Pigment nacré multicolore à effet scintillant amélioré et procédé de préparation associé
WO2020184996A2 (fr) Précurseur de cuivre de frittage de lumière, son procédé de fabrication et son procédé de frittage de lumière
WO2016167474A1 (fr) Réseau de faisceaux de nanofils, film optique à large bande ultra-haute performance, et procédé de sa fabrication
WO2023243888A1 (fr) Pièce en céramique résistante à la gravure et son procédé de fabrication
WO2020130644A2 (fr) Tôle d'acier électrique à grains non orientés et son procédé de production
WO2022031005A1 (fr) Couche de résine, procédé de préparation de couche de résine et panneau à cristaux liquides
WO2022196902A1 (fr) Structure de séparateur, son procédé de production et batterie secondaire l'utilisant
WO2020209544A1 (fr) Composition nano-inorganique et procédé de revêtement l'utilisant
WO2021015474A1 (fr) Composant d'appareil de gravure au plasma destiné à fabriquer un semiconducteur comprenant un corps fritté composite et son procédé de fabrication

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21894790

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21894790

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 30/11/2023)