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US20210231394A1 - Metal members - Google Patents

Metal members Download PDF

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Publication number
US20210231394A1
US20210231394A1 US17/147,457 US202117147457A US2021231394A1 US 20210231394 A1 US20210231394 A1 US 20210231394A1 US 202117147457 A US202117147457 A US 202117147457A US 2021231394 A1 US2021231394 A1 US 2021231394A1
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US
United States
Prior art keywords
aluminum sheet
engine oil
metal member
examples
comparative example
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Abandoned
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US17/147,457
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English (en)
Inventor
Norio Inami
Kenichi KOHASHI
Hiroki Habazaki
Akira Koyama
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Hokkaido University NUC
Toyota Motor Corp
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Hokkaido University NUC
Toyota Motor Corp
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Assigned to NATIONAL UNIVERSITY CORPORATION HOKKAIDO UNIVERSITY, TOYOTA JIDOSHA KABUSHIKI KAISHA reassignment NATIONAL UNIVERSITY CORPORATION HOKKAIDO UNIVERSITY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HABAZAKI, HIROKI, INAMI, NORIO, KOHASHI, Kenichi, KOYAMA, AKIRA
Publication of US20210231394A1 publication Critical patent/US20210231394A1/en
Abandoned legal-status Critical Current

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
    • F28F21/081—Heat exchange elements made from metals or metal alloys
    • F28F21/082—Heat exchange elements made from metals or metal alloys from steel or ferrous alloys
    • F28F21/083—Heat exchange elements made from metals or metal alloys from steel or ferrous alloys from stainless steel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/12—Light metals
    • C23G1/125—Light metals aluminium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/22—Light metals
    • 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
    • C25D11/18—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
    • C25D11/246—Chemical after-treatment for sealing layers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
    • F28F13/003—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by using permeable mass, perforated or porous materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
    • F28F13/18—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by applying coatings, e.g. radiation-absorbing, radiation-reflecting; by surface treatment, e.g. polishing
    • F28F13/185—Heat-exchange surfaces provided with microstructures or with porous coatings
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
    • F28F21/081—Heat exchange elements made from metals or metal alloys
    • F28F21/084—Heat exchange elements made from metals or metal alloys from aluminium or aluminium alloys
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
    • F28F21/081—Heat exchange elements made from metals or metal alloys
    • F28F21/086—Heat exchange elements made from metals or metal alloys from titanium or titanium alloys
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D21/00—Heat-exchange apparatus not covered by any of the groups F28D1/00 - F28D20/00
    • F28D2021/0019—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for
    • F28D2021/008—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for for vehicles
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D21/00—Heat-exchange apparatus not covered by any of the groups F28D1/00 - F28D20/00
    • F28D2021/0019—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for
    • F28D2021/008—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for for vehicles
    • F28D2021/0082—Charged air coolers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2245/00—Coatings; Surface treatments
    • F28F2245/02—Coatings; Surface treatments hydrophilic

Definitions

  • the present disclosure relates to metal members.
  • SLIPS Slippery Liquid-Infused Porous Surface
  • a rough surface with low surface free energy improves the wetness of lubricant oils and prevents firm sticking of liquids to the solid surface, so that droplets that have stuck onto lubricant oil films have high mobility and easily slide down even gentle slopes.
  • SLIPS have such features, they are not only useful as liquid-repellent, antifouling and corrosion-resistant surfaces, but are also expected to allow applications and deployments that have been difficult to achieve with conventional super-water-repellent or super-oil-repellent surfaces, including applications for ice-resistant surfaces that prevent sticking of ice, biological contaminant-resistant surfaces that prevent sticking of biological liquids such as blood, and water harvest technologies that utilize the high droplet-aggregating properties of lubricant oil films.
  • Liquid repellency for a variety of metal oxide surfaces has also been in great demand in the industry.
  • SAM self-assembled monolayer
  • Phosphonic acid derivatives which have come to be widely used in recent years, are highly stable compounds that form denser and more stable SAMs than conventionally known silane coupling agents.
  • SAM surface treatment for reduction of surface free energy on metal oxide surfaces has been considered to be essential for causing stuck liquids to slide off.
  • the present inventors have in fact found that even when using lubricant oils composed of fluorine-based polymers, or silicone oils, that are well known as SLIPS lubricant oils, sticking of water cannot be prevented unless SAM surface treatment is also carried out.
  • ZnDTP zinc dialkyldithiophosphate
  • ZnDTP zinc dialkyldithiophosphate
  • FIG. 1A is a scanning electron microscope (SEM) image of the surface of an aluminum sheet with a porous surface.
  • FIG. 1B is a scanning electron microscope (SEM) image of the surface of an aluminum sheet with a hierarchically structured porous surface.
  • FIG. 1C is a diagram showing contact angles of water droplets and automobile engine oil droplets on the surfaces of each of the aluminum sheets of Reference Examples 1 to 4.
  • FIG. 2A is a graph showing the relationship between aluminum sheet rotational speed and automobile engine oil residue amount (rotation time: 60 seconds), for each of the aluminum sheets of Examples 1 and 2 and Comparative Example 5.
  • FIG. 2B is a graph showing the relationship between aluminum sheet rotational speed and 10 ⁇ L water droplet falling angle (rotation time: 60 seconds), for each of the aluminum sheets of Examples 1 and 2 and Comparative Example 5.
  • FIG. 2C is a graph showing the relationship between automobile engine oil residue amount and 10 ⁇ L water droplet falling angle (rotation times: 10, 60 and 300 seconds), for each of the aluminum sheets of Examples 1 and 2 and Comparative Example 5.
  • FIG. 3 is a graph showing the relationship between liquid mixture immersion time and 10 ⁇ L water droplet falling angle, for the aluminum sheets of Examples 1 and 2 and Comparative Examples 5 and 7.
  • FIG. 4 is a graph showing weight change after a corrosion resistance test for the aluminum sheets of Examples 1 and 2 and Comparative Examples 1 to 6.
  • FIG. 5A is a scanning electron microscope (SEM) image of the surface of an anodized aluminum sheet without hierarchical structuring, before a corrosion resistance test.
  • FIG. 5B is a scanning electron microscope (SEM) image of the surface of the aluminum sheet of Comparative Example 5 after the corrosion resistance test.
  • FIG. 5C is a scanning electron microscope (SEM) image of the surface of the aluminum sheet of Comparative Example 3 after the corrosion resistance test.
  • FIG. 5D is a scanning electron microscope (SEM) image of the surface of the aluminum sheet of Example 1 after the corrosion resistance test.
  • FIG. 5E is a scanning electron microscope (SEM) image of the surface of the aluminum sheet of Comparative Example 1 after the corrosion resistance test.
  • FIG. 6A is a scanning electron microscope (SEM) image of the surface of a hierarchically structured and anodized aluminum sheet, before a corrosion resistance test.
  • SEM scanning electron microscope
  • FIG. 6B is a scanning electron microscope (SEM) image of the surface of the aluminum sheet of Comparative Example 6 after the corrosion resistance test.
  • FIG. 6C is a scanning electron microscope (SEM) image of the surface of the aluminum sheet of Comparative Example 4 after the corrosion resistance test.
  • FIG. 6D is a scanning electron microscope (SEM) image of the surface of the aluminum sheet of Example 2 after the corrosion resistance test.
  • FIG. 6E is a scanning electron microscope (SEM) image of the surface of the aluminum sheet of Comparative Example 2 after the corrosion resistance test.
  • FIG. 7 is a diagram illustrating the method of fabricating the aluminum sheet of Reference Example 5.
  • FIG. 8A is a diagram showing the state of the surface of the aluminum sheet of Reference Example 5 and the contact angle upon placement of a 10 ⁇ L water droplet.
  • FIG. 8B is a diagram showing the state of the surface of the aluminum sheet of Reference Example 6 and the contact angle upon placement of a 10 ⁇ L water droplet.
  • FIG. 9A is a graph showing X-ray photoelectron spectroscopy (XPS) analysis results for the surface of the aluminum sheet of Reference Example 5, after automobile engine oil immersion and cleaning.
  • XPS X-ray photoelectron spectroscopy
  • FIG. 9B is a graph showing X-ray photoelectron spectroscopy (XPS) analysis results for the surface of the aluminum sheet of Reference Example 5, after automobile engine oil immersion and cleaning.
  • XPS X-ray photoelectron spectroscopy
  • FIG. 9C is a graph showing X-ray photoelectron spectroscopy (XPS) analysis results for the surface of the aluminum sheet of Reference Example 5, after automobile engine oil immersion and cleaning.
  • XPS X-ray photoelectron spectroscopy
  • FIG. 10 is a graph showing electrochemical measurement results for the aluminum sheets of Examples 3 to 5 and Comparative Example 8.
  • FIG. 11 is a graph showing electrochemical measurement results for the aluminum sheets of Example 3 and Comparative Examples 8 to 10.
  • a metal member of the disclosure has a porous surface, with the porous surface directly covered by a hydrocarbon-based oil comprising zinc dialkyldithiophosphate (ZnDTP).
  • ZnDTP zinc dialkyldithiophosphate
  • the metal member has a porous surface.
  • a porous surface is a porous layer formed on the surface of a metal member, and for example, it may be an oxidized surface with an oxide of the same type of metal as the metal member. More specifically, the porous surface may be an anodized surface.
  • the anodized surface can be obtained by anodization of the metal member, and when the metal member is an Al member, for example, it can be obtained by alumite treatment, and more specifically by surface treatment that produces an oxide layer (Al 2 O 3 ) by electrolysis using Al as the anode (positive electrode).
  • Alumite treatment can be carried out according to JIS H8601 or JIS H8603, for example, although another method may also be used.
  • the thickness and pore sizes of the porous surface are not particularly restricted.
  • the thickness of the porous surface can be appropriately adjusted according to the purpose of use of the metal member.
  • the form of the porous surface is not restricted so long as it is a slippery liquid surface (SLIPS).
  • the pore sizes (diameters) of each of the pores of the porous surface are preferably 1 nm to 5 ⁇ m.
  • the porous surface may have a microscale irregular structure, a nanoscale irregular structure or a mixture of such structures, or a hierarchical structure comprising them.
  • the pore sizes (diameters) of each of the pores of the porous surface may be 0.1 ⁇ m to 5 ⁇ m, but they are preferably 0.1 ⁇ m to 0.5 ⁇ m.
  • the pore sizes (diameters) of each of the pores of the porous surface may be 1 nm to 100 nm, but they are preferably 30 nm to 100 nm.
  • the material of the metal member may be any metal that is able to form a porous surface, and for example, the metal member may be a member composed of Al, Ti, Fe or Mg, or an alloy of any of those metals, or stainless steel.
  • the metal member may be a member for any desired purpose of use, such as a vehicle member, and more specifically an automobile member.
  • the metal member is an automobile member, it is preferably a part to which engine oil is to be supplied.
  • engine oil as the hydrocarbon-based oil
  • the metal member When the metal member is an automobile member, the metal member may be an intercooler member.
  • An intercooler is a unit with inflow of high-temperature air, and since exhaust gas also flows in due to the construction of the automobile, it is one unit of the automobile whose members are especially prone to corrosion.
  • One such member for example, is the heat exchanger.
  • the corrosion resistance of the intercooler can therefore be improved by applying a metal member according to this disclosure, for such members.
  • the hydrocarbon-based oil includes at least zinc dialkyldithiophosphate (ZnDTP).
  • ZnDTP zinc dialkyldithiophosphate
  • the hydrocarbon-based oil may be a paraffinic oil or a polyalphaolefin.
  • the hydrocarbon-based oil may be a lubricant oil, specifically an engine oil, and more specifically an engine oil for an automobile.
  • zinc dialkyldithiophosphate When included in a hydrocarbon-based oil, zinc dialkyldithiophosphate (ZnDTP) imparts water-repellency to the surface of the metal member. More specifically, it is thought that when a hydrocarbon-based oil containing zinc dialkyldithiophosphate (ZnDTP) is coated onto a metal member, it is chemically adsorbed onto the surface of the metal member, forming a liquid-repellent coated film.
  • the concentration of the zinc dialkyldithiophosphate (ZnDTP) may be 0.1 mass % to 30.0 mass % with respect to the hydrocarbon-based oil.
  • the concentration of the zinc dialkyldithiophosphate (ZnDTP) may be 0.1 mass % or greater, 1.0 mass % or greater, 2.0 mass % or greater or 5.0 mass % or greater, and 30.0 mass % or lower, 20.0 mass % or lower, 10.0 mass % or lower or 5.0 mass % or lower.
  • Metal members for Reference Examples 1 to 4 were fabricated and evaluated for liquid repellency, in the following manner.
  • a 99.5% aluminum (Al) sheet was cut out to a size of 20 mm ⁇ 50 mm and subjected to acetone degreasing by ultrasonic cleaning for 10 minutes. It was then immersed for 120 seconds in a 1.0 M NaOH aqueous solution (60° C.) to remove the oxide layer, and then immersed for 180 seconds in a 1.0 M HNO 3 aqueous solution (60° C.) to remove the smut produced in the previous step.
  • anodization was carried out in a 0.3 M H 2 SO 4 aqueous solution (15° C.) for 180 seconds with a voltage of 25 V between the polar plates, forming an anodized layer having pores on the nanometer scale.
  • the procedure was carried out in a two-electrode system with this sheet as the working electrode and a separate Al sheet as the counter electrode.
  • oxygen plasma treatment was carried out for 4 minutes for cleaning of the surface, to obtain an aluminum sheet having a porous anodized surface.
  • An aluminum sheet with a hierarchical structure was obtained in the same manner as Reference Example 1, except that chemical etching was carried out before anodization, forming etch pits on the micrometer scale.
  • the aluminum sheet of Reference Example 1 was subjected to oxygen plasma treatment, and then immersed for 2 days in an ethanol solution containing 1 mM CF 3 (CF 2 ) 7 PO(OH) 2 (perfluorooctylphosphonic acid, FOPA), and finally heat treated for 1 hour in an air atmosphere (100° C.), to form a self-assembled monolayer (SAM) on the surface of the aluminum sheet of Reference Example 1.
  • OPA perfluorooctylphosphonic acid
  • a self-assembled monolayer was formed on the surface of the aluminum sheet of Reference Example 2 having a hierarchical structure, in the same manner as Reference Example 3, except for using the aluminum sheet of Reference Example 2 instead of the aluminum sheet of Reference Example 1.
  • Each of the aluminum sheets of Reference Examples 1 to 4 were measured for water droplet or automobile engine oil droplet contact angle.
  • FIG. 1A is a scanning electron microscope (SEM) image of the aluminum sheet of Reference Example 1.
  • SEM scanning electron microscope
  • FIG. 1A a porous Al 2 O 3 layer had formed on the surface of the aluminum sheet of Reference Example 1 by anodization.
  • FIG. 1B micrometer-scale pits produced by etching and a hierarchical structure due to the porous Al 2 O 3 layer had been formed on the surface of the aluminum sheet of Reference Example 2.
  • the aluminum sheets of Reference Examples 1 and 2 which had not formed a self-assembled monolayer (SAM) were super hydrophilic, having water droplet contact angles of 4.6 ⁇ 1.2 and approximately 0, respectively.
  • the aluminum sheets of Reference Examples 3 and 4 which had formed self-assembled monolayers (SAM) had high water-repellency, with water droplet contact angles of 129.1 ⁇ 0.8 and 161.7 ⁇ 1.0, respectively.
  • the contact angle was a large value of 158.2 ⁇ 1.5, with high liquid repellency for automobile engine oil droplets, whereas in Reference Examples 1 to 3 the contact angle was 90°, which was low liquid repellency.
  • Aluminum sheets for Examples 1 and 2 and Comparative Examples 5 to 7 were fabricated and their performance evaluated, in the following manner.
  • a 100 ⁇ L portion of the automobile engine oil was measured out, coated onto the surfaces of each of the aluminum sheets of Reference Examples 1 to 4 and allowed to stand for 10 minutes or longer, to obtain aluminum sheets for Examples 1 and 2 and for Comparative Examples 5 and 6.
  • An aluminum sheet for Comparative Example 7 was obtained in the same manner as Example 1, except for coating the automobile engine oil on an aluminum sheet lacking hierarchical structuring by etching, porosity by anodization and SAM coating formation.
  • Examples 1 and 2 and Comparative Example 5 were evaluated for automobile engine oil retentivity and liquid sliding properties in an environment with shear force applied to the automobile engine oil. This served to simulate reduction of SLIPS in an environment causing loss of lubricant oil due to gravity or wind.
  • each of the aluminum sheets of Examples 1 and 2 and Comparative Example 5 were rotated using a spin coater under conditions with a rotational speed of 500 rpm to 7000 rpm and a rotation time of 10 seconds to 300 seconds. The weight of the remaining automobile engine oil and the 10 ⁇ L water droplet falling angle were then measured.
  • FIG. 2A is a graph showing the relationship between aluminum sheet rotational speed and automobile engine oil residue amount (rotation time: 60 seconds), for each of the aluminum sheets of Examples 1 and 2 and Comparative Example 5
  • FIG. 2B is a graph showing the relationship between aluminum sheet rotational speed and 10 ⁇ L water droplet falling angle (rotation time: 60 seconds), for each of the aluminum sheets of Examples 1 and 2 and Comparative Example 5
  • FIG. 2C is a graph showing the relationship between automobile engine oil residue amount and 10 ⁇ L water droplet falling angle (rotation times: 10, 60 and 300 seconds), for each of the aluminum sheets of Examples 1 and 2 and Comparative Example 5.
  • the residue amount was especially large with the aluminum sheet of Example 2 which had a hierarchical structure. This is attributed to the aluminum sheet with a hierarchical structure having micrometer-scale irregularities in which the automobile engine oil was retained.
  • Example 1 Comparison between the aluminum sheets of Example 1 and Comparative Example 5 which did not have a hierarchical structure showed no significant difference in automobile engine oil residue amount.
  • Example 2 The reason that the water droplet falling angle particularly tended to increase with the aluminum sheet of Example 2 is thought to be because the originally smooth lubricant oil film reflected greater roughness of the surface as the lubricant oil was lost, leading to roughening of the lubricant oil film and increased contact area with the water droplets.
  • Example 1 Based on the relationship between the automobile engine oil residue amount and 10 ⁇ L water droplet falling angle as well, the smallest water droplet falling angle (satisfactory water-repellency) even with the same lubricant oil residue amount, was exhibited by the aluminum sheet of Example 1 which did not have a hierarchical structure and lacked a SAM coating.
  • Acetic acid and a 10 g/L NaCl aqueous solution were stirred at 1000 rpm to prepare a liquid mixture.
  • the aluminum sheets of Examples 1 and 2 and Comparative Examples 3 and 7 were each immersed in the liquid mixture and removed after a predetermined time period had elapsed.
  • the 10 ⁇ L water droplet falling angle of the aluminum sheet of each example was then measured.
  • the coating amount of the automobile engine oil on the aluminum sheet of each example was 3.75 ⁇ L/cm 2 .
  • FIG. 3 is a graph showing the relationship between liquid mixture immersion time and 10 ⁇ L water droplet falling angle, for each of the aluminum sheets of Examples 1 and 2 and Comparative Examples 5 and 7.
  • Example 1 which lacked a SAM coating.
  • Example 2 which had a hierarchical structure and lacked a SAM coating tended to have the greatest increase in water droplet falling (i.e. reduction in water-repellency), exceeding 20° in a shorter time than the aluminum sheet of Comparative Example 7, which was a smooth aluminum sheet lacking both hierarchical structuring and porosity and coated with an automobile engine oil.
  • the aluminum sheet of each example was immersed for 5 days in the aforementioned liquid mixture and the weight change and surface form change of the sheet were observed.
  • FIG. 4 is a graph showing weight change after a corrosion resistance test for the aluminum sheets of Examples 1 and 2 and Comparative Examples 1 to 6.
  • the weight was reduced by about 0.5 mg/cm 2 to 1.5 mg/cm 2 with all of the aluminum sheets of Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4, which were not coated with automobile engine oil. This occurred due to dissolution of aluminum by corrosion.
  • Example 1 and Example 2 and Comparative Examples 5 and 6 which were coated with automobile engine oil, all of the weight changes were 0.1 mg/cm 2 or less, and therefore weight reduction by corrosion was inhibited.
  • Example 2 and Comparative Example 5 and Comparative Example 6 there was a slight increase in weight after the corrosion resistance test. This occurred due to trace white product residue after the corrosion test even after cleaning of the aluminum sheets with an organic solvent such as acetone.
  • the white product is thought to be the reaction product between the solution mixture and the neutralizing agent included among the additives of the automobile engine oil.
  • FIG. 5A is a scanning electron microscope (SEM) image of the surface of an anodized aluminum sheet without hierarchical structuring, before a corrosion resistance test
  • FIGS. 5B to 5E are scanning electron microscope (SEM) images of the surfaces of the aluminum sheets of Comparative Example 5, Comparative Example 3, Example 1 and Comparative Example 1, in that order, after the corrosion resistance test.
  • FIG. 6A is a scanning electron microscope (SEM) image of the surface of an anodized aluminum sheet with hierarchical structuring, before a corrosion resistance test
  • FIGS. 6B to 6E are scanning electron microscope (SEM) images of the surfaces of the aluminum sheets of Comparative Example 6, Comparative Example 4, Example 2 and Comparative Example 2, in that order, after the corrosion resistance test.
  • Automobile engine oil was coated onto an aluminum sheet with a porous surface (12.5 ⁇ L/cm 2 ) and allowed to stand for 24 hours, as illustrated in FIG. 7 .
  • the aluminum sheet was then subjected to ultrasonic cleaning in heptane and dried to obtain an aluminum sheet for Reference Example 5.
  • An aluminum sheet for Reference Example 6 was obtained in the same manner as Reference Example 5, except that it was not coated with automobile engine oil.
  • the surface states of the aluminum sheets of Reference Examples 5 and 6 were observed with a scanning electron microscope (SEM). A 10 ⁇ L water droplet was placed on each aluminum sheet and the contact angle was measured. The surface of the aluminum sheet of Reference Example 5 after automobile engine oil immersion and cleaning was analyzed by X-ray photoelectron spectroscopy (XPS).
  • SEM scanning electron microscope
  • XPS X-ray photoelectron spectroscopy
  • FIGS. 8A and 8B are diagrams showing the surface states of the aluminum sheets of Reference Examples 5 and 6, respectively, and the contact angles upon placement of 10 ⁇ L water droplets.
  • FIGS. 9A to 9C are graphs showing X-ray photoelectron spectroscopy (XPS) analysis results for the surface of the aluminum sheet of Reference Example 5, after automobile engine oil immersion and cleaning.
  • XPS X-ray photoelectron spectroscopy
  • Aluminum sheets for Examples 3 to 5 and Comparative Examples 8 to 10 were fabricated and their corrosion resistance evaluated, in the following manner.
  • An aluminum sheet having a porous anodized surface was fabricated in the same manner as Reference Example 1.
  • the aluminum sheet was coated with oil comprising zinc dialkyldithiophosphate (ZnDTP) added to a base oil, to fabricate an aluminum sheet for Example 3.
  • ZnDTP zinc dialkyldithiophosphate
  • the amount of zinc dialkyldithiophosphate (ZnDTP) in the oil was 2 mass % with respect to the total oil.
  • Aluminum sheets for Examples 4 and 5 were fabricated in the same manner as Example 3, except that the amount of zinc dialkyldithiophosphate (ZnDTP) in the oil was changed to 10 mass % and 20 mass %, respectively.
  • ZnDTP zinc dialkyldithiophosphate
  • An aluminum sheet having a porous anodized surface was fabricated in the same manner as Reference Example 1.
  • the aluminum sheet was coated with a base oil to fabricate an aluminum sheet for Comparative Example 8.
  • An aluminum sheet for Comparative Example 9 was fabricated in the same manner as Example 3, except for using an oil comprising calcium sulfonate instead of zinc dialkyldithiophosphate (ZnDTP) added to a base oil.
  • the amount of calcium sulfonate in the oil was 1 mass % with respect to the total oil.
  • An aluminum sheet for Comparative Example 10 was fabricated in the same manner as Comparative Example 9, except that the amount of calcium sulfonate in the oil was changed to 10 mass %.
  • the aluminum sheets of Examples 3 to 5 and Comparative Examples 8 to 10 were evaluated for corrosion resistance by electrochemical measurement.
  • FIG. 10 is a graph showing electrochemical measurement results for the aluminum sheets of Examples 3 to 5 and Comparative Example 8.
  • the aluminum sheet of Comparative Example 8 which was coated with a base oil without addition of zinc dialkyldithiophosphate (ZnDTP) exhibited high anode current density, and a sufficient corrosion-inhibiting effect could not be obtained.
  • the aluminum sheets of Examples 3 to 5, which were coated with oils comprising zinc dialkyldithiophosphate (ZnDTP) added to base oils exhibited current density of at least four digits lower than the aluminum sheet of Comparative Example 8, or in other words, excellent corrosion resistance.
  • FIG. 11 is a graph showing electrochemical measurement results for the aluminum sheets of Example 3 and Comparative Examples 8 to 10.
  • the aluminum sheet of Comparative Example 8 which was coated with a base oil, and the aluminum sheets of Comparative Examples 9 and 10 which had calcium sulfonate added instead of zinc dialkyldithiophosphate (ZnDTP), exhibited high anode current density, and a sufficient corrosion-inhibiting effect had not been obtained.
  • ZnDTP zinc dialkyldithiophosphate

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