EP2818579A1 - Metallmaterial und oberflächenbehandlungsverfahren sowie vorrichtung - Google Patents

Metallmaterial und oberflächenbehandlungsverfahren sowie vorrichtung Download PDF

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Publication number
EP2818579A1
EP2818579A1 EP13752521.8A EP13752521A EP2818579A1 EP 2818579 A1 EP2818579 A1 EP 2818579A1 EP 13752521 A EP13752521 A EP 13752521A EP 2818579 A1 EP2818579 A1 EP 2818579A1
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Prior art keywords
cathode electrode
metallic material
protrusions
target
metal substrate
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EP13752521.8A
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English (en)
French (fr)
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EP2818579A4 (de
Inventor
Masayasu Nagoshi
Kaoru Sato
Hisato Noro
Kazuhiko Baba
Seiichi Watanabe
Souki Yoshida
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JFE Steel Corp
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JFE Steel Corp
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Publication date
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Publication of EP2818579A1 publication Critical patent/EP2818579A1/de
Publication of EP2818579A4 publication Critical patent/EP2818579A4/de
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
    • C25F3/06—Etching of iron or steel

Definitions

  • the present invention relates to a metallic material, a method for a surface treatment of a metallic material, a method for manufacturing a water-repellent material using a metallic material as a base, a surface treatment apparatus for an electroconductive material, and a method for a surface treatment of an electroconductive material.
  • Non Patent Literature 1 Hideaki TAKAHASHI; Masatoshi SAKAIRI; Tatsuya KIKUCHI; and Himendra JHA, Hyomen Gijutsu, vol. 60 (2009) No. 3, p. 14
  • Non Patent Literature 2 Wataru NATSU, "Application and Theory of Micro Electrochemical Machining,” Hyomen Gijutsu, vol. 61 (2010) No. 4, p. 294 Summary
  • the surface of the metallic material has the effects of improving workability by oil retention, and giving uniform surface appearance, it exhibits no new function.
  • a method for improving coating adhesion of outer plates for automobiles a method has been proposed that forms phosphoric crystals on the surface of a metallic material.
  • the particle diameter of the phosphoric crystals formed by this method has a size of a few microns. Given this situation, the metallic material surface exhibits no new function.
  • Non Patent Literature 1 forms microscopic pours on the surface, which limits functions to be imparted.
  • the surface becomes an oxidized layer, and the surface properties are limited by the type of oxides.
  • Electromechanical machining method disclosed in Non Patent Literature 2 demands to remarkably reduce the distance between a target surface and a counter electrode close as much as possible in order to form surface microstructures, but the control is extremely difficult.
  • the present invention has been achieved in view of the above circumstances, and an object thereof is to provide a metallic material having new functions such as hydrophilic properties and luminescence properties.
  • Still another object of the present invention is to provide method and apparatus for forming nano-level microstructures in a surface specific part or in a surface wide area of an electroconductive material at a low cost and efficiency.
  • a metallic material according to the present invention includes: a metal substrate; and a modified layer formed on a surface of the metal substrate, wherein the modified layer includes three or more protrusions in an area of 10 ⁇ m 2 on average protruding from the surface of the metal substrate, the protrusions having an average diameter of 1 ⁇ m or less when viewed in a direction perpendicular to the surface of the metal substrate.
  • the modified layer includes, in an area of 10 ⁇ m 2 on average, one or more protrusions including a base part protruding from the surface of the metal substrate and a tip part formed on the end of the base part, the protrusions having an average diameter of 1 ⁇ m or less when viewed in a direction perpendicular to the surface of the metal substrate and a constricted structure with the outer diameter of the base part being smaller than the outer diameter of the tip part.
  • the average diameter of the protrusions is 500 nm or less when viewed in a direction perpendicular to the surface of the metal substrate.
  • positions on which the protrusions are formed have no periodicity in the in-plane direction of the metal substrate.
  • the modified layer includes recesses having an average diameter of 500 nm or less when viewed in a direction perpendicular to the surface of the metal substrate.
  • the metal substrate is formed of alloy steel.
  • the metal substrate is formed of a steel material.
  • the metal substrate has a composition different from that of the protrusions.
  • a method for surface treatment of a metallic material includes: immersing a target material as a cathode electrode formed of a metallic material having a target surface and an anode electrode into an electrolytic solution; applying a voltage that is 70 V or more and is in such a range that does not oxidize or melt the target material between the cathode electrode and the anode electrode to form microstructures on the target surface; taking the target material out of the electrolytic solution and washing the target material; and performing a water-repellent treatment on the target surface of the washed target material.
  • a method for surface treatment of a metallic material includes: immersing a target material as a cathode electrode formed of a metallic material having a target surface and an anode electrode into an electrolytic solution; applying a voltage of 70 V or more and 200 V or less between the cathode electrode and the anode electrode to form microstructures on the target surface; taking the target material out of the electrolytic solution and washing the target material; and performing a water-repellent treatment on the target surface of the washed target material.
  • a method for manufacturing a water-repellent material using a metallic material as a base includes: immersing a metallic material as a target material as a cathode electrode having a target surface and an anode electrode into an electrolytic solution; applying a voltage of 70 V or more and 200 V or less between the cathode electrode and the anode electrode to form microstructures on the surface of the metallic material as the target material; taking the metallic material out of the electrolytic solution and washing the metallic material; and performing a water-repellent treatment on the target surface of the washed metallic material.
  • the above-described surface treatment apparatus for an electroconductive material according to the present invention further includes a mechanism that changes the position of the opening and/or the relative positions of the anode electrode and the cathode electrode.
  • the power supply applies a voltage of 60 V or more and 300 V or less between the anode electrode and the cathode electrode.
  • the shield is an insulating heat-resistant material provided with the opening that is covered with the surface of the cathode electrode.
  • the electroconductive material is a metallic material.
  • the surface treatment apparatus and a method for surface treatment of an electroconductive material according to the present invention can manufacture an electroconductive material formed with nano-level microstructures in a surface specific part or in a surface wide area at low cost and efficiently.
  • FIGS. 1A and 1B are a plan view illustrating a structure of a metallic material as an embodiment according to the present invention and A-A line cross-sectional view of FIG. 1A , respectively.
  • this metallic material 1 as an embodiment according to the present invention includes a base 2 and protrusions 3 as a modified layer formed on the surface of the base 2.
  • the base 2 is formed of a metallic material.
  • the metallic material may include alloy steel including stainless steel, steel sheets such as cold-rolled steel sheets containing Fe, C, and alloy elements as needed in a minute amount such as 3% by mass or less, mild steel sheets, high-strength steel sheets with a tensile strength of around 2 GPa, and hot-rolled steel sheets.
  • Examples of the shape of the base 2 may include, but not limited to, a sheet shape, a rod shape, a line shape, and a pipe shape.
  • the base 2 may be constructed by welding plural pieces.
  • its sheet thickness is not limited; available are from a metallic foil with a thickness of 100 ⁇ m or less to a thick steel sheet with a thickness of 3 mm or more.
  • the protrusions 3 are formed from microstructures protruding from the surface of the base 2 having an average diameter R of 1 ⁇ m and preferably 500 nm or less when viewed in a direction perpendicular to the surface of the base 2.
  • FIG. 2 is a scanning electron microscope (SEM) photograph illustrating an example of protrusions formed on the surface of a cold-rolled steel sheet. In the photograph, the objects indicated by the arrows are the protrusions 3.
  • the protrusions 3 were formed by applying a voltage of 135 V for 30 minutes in an aqueous K 2 CO 3 solution with a concentration of 0.3 mol/L between the cold-rolled steel sheet and a platinum electrode as a cathode electrode and an anode electrode, respectively.
  • the in-plane distribution of the protrusions 3 is not limited, not having specific periodicity is advantageous in manufacture.
  • the protrusions 3 when the protrusions 3 have a structure in which the outer diameter Lrmin of a base part 3a is smaller than the outer diameter Lrmax of a tip part 3b, that is a constricted structure, the specific surface area and internal pours of the base 2 become apparently larger than a structure having no constricted structure. This can further improve hydrophilic properties, which are influenced by the specific surface area. It can be expected that the protrusions 3 having the constricted structure have the effects of imparting chemical reactions on the surface and facilitating functions therefor to the surface of the base 2 and improving adhesion of a thin film layer formed on the surface of the base 2.
  • V Voltage (V)*time (minutes) Depth from liquid surface (mm) Average protrusion diameter (nm) Protrusion density (pieces/10 ⁇ m 2 )
  • V Voltage
  • nm Average protrusion diameter
  • Protrusion density pieces/10 ⁇ m 2
  • SUS316 stainless steel (1 mm thickx2.5 mm widex30 mm long) was used. The surface was mirror-polished with Dia-Lap ML-150P. This stainless steel and Pt as a cathode electrode and an anode electrode, respectively, were immersed into an aqueous K 2 CO 3 solution with a concentration of 0.1 mol/L, and different application voltages were applied between the cathode electrode and the anode electrode for 15 minutes to prepare specimens. The electrode (SUS316 stainless steel) after the experiment was thoroughly rinsed with distilled water and thoroughly dried. A contact angle measurement experiment was performed for the surface at three parts with a depth from the liquid surface of 30 mm, 28 mm, and 26 mm.
  • the electrolytic solution 12 is, but not limited to, a solution that has electroconductivity and, during the surface treatment on the surface of the target material 14, hardly etches the surface of the target material 14 excessively, adheres to or precipitates on the surface of the anode electrode 13 and the target material 14, and forms a sediment.
  • the anode electrode 13 is formed of a material that is thermally and chemically stable on discharge. Examples of the anode electrode 13 may include Pt, Ir, and graphite.
  • the target material 14 is not limited so long as it is a metallic material.
  • examples of the steel material may include cold-rolled materials, hot-rolled materials, cast materials, and machined (including welded) objects thereof.
  • the type of the steel is not limited; examples of the steel may include carbon steel, low-alloy steel, and stainless steel. Other examples may include plated steel sheets such as electrogalvanized steel sheets.
  • the shape of the target material 14 is not limited and may be formed in a sheet shape, a wire shape, a rod shape, or a pipe shape, or may be a machined component.
  • the target material 14 is required to be immersed into the electrolytic solution 12 and is required to be at least deeper from the liquid surface by 1 mm or more.
  • the discharge voltage is required to be a voltage that forms microscopic protrusions on the surface of a steel material.
  • a voltage less than a lower limit voltage does not form the microscopic protrusions on the surface, and the lower limit can be determined by observing the presence or absence of the microscopic protrusions with a SEM.
  • the voltage exceeds an upper limit, the target surface melts.
  • a voltage at which the surface melts can be therefore determined as the upper limit.
  • the upper limit can be determined easily by examining a voltage at which the surface is oxidized using a SEM and an energy-dispersive X-ray spectrometer (EDS) attached to the SEM.
  • EDS energy-dispersive X-ray spectrometer
  • a discharge treatment time is required to be 3 seconds or more. Although the discharge treatment time may be such a long time as 60 minutes, a discharge treatment time of 30 minutes or more is not preferable, because a too long discharge treatment time may wear the target material 14. It is known that within the desirable voltage range a higher application voltage provides higher water-repellent properties of a surface after the final process. The most preferable condition is therefore to select an application voltage close to the upper limit of the preferable condition range.
  • FIG. 13 is an example of a treated SUS316L stainless steel sheet with a thickness of 0.8 mm.
  • This SUS316L stainless steel sheet was cut to 2 mm wide and 30 mm long and was given conduction through a copper wire to form a cathode electrode.
  • a Pt wire with a length of 50 cm was bent to form a planar shape so as to avoid mutual contact.
  • a heat-resistant resin was heat-crimped to a connecting part between the SUS316L stainless steel sheet and the copper wire, and a part with a length of 20 mm of the electrode was immersed into an electrolytic solution so that the copper wire will not be in contact with the electrolytic solution.
  • An aqueous K 2 CO 3 solution with a concentration of 0.1 mol/L was used as the electrolytic solution and discharge was performed for 10 minutes with the voltage set to be 130 V. Immediately after that, the electrode was washed with water.
  • Step S3 a water-repellent treatment is performed on the target surface of the washed target material 14 (Step S3).
  • the method of washing which is performed in order to remove the electrolytic solution on the surface, may include immersion into or spraying pure water. Without limited to pure water, weak acids or alkaline solutions may be used so long as the microstructures on the surface are not damaged. During the process, electrolysis may be applied. After the washing, the target surface may be dried or may not be dried and advanced to the next process depending on the subsequent water-repellent treatment.
  • FIG. 14 is a side-view observation of a state after the water-repellent treatment was performed on the specimen surface illustrated in FIG. 13 and distilled water was dropped thereon. From this observation, it has been measured that the contact angle of water is 152° and it has been found out that super water repellency is achieved.
  • the contact angle of water for a specimen without the water-repellent treatment performed was 51°.
  • a similar water-repellent treatment was performed on a material without performing in-liquid plasma discharge, and the contact angle of water for the material was 125°. It has been thus found out that both the in-liquid plasma discharge and the water-repellent treatment are required to obtain a super water-repellent surface.
  • the inventors of the present invention has considered a method for manufacturing nano-level microstructures on a specific part in the surface of the electroconductive material and has found out that the nano-level microstructures can be formed on the specific part in the surface of the electroconductive material by immersing a part to be treated of the electroconductive material into an electrolytic solution together with an anode electrode and placing a shield having an opening between the electroconductive material and the anode electrode.
  • the inventors of the present invention has further found out that the nano-level microstructures can be formed on the surface of the electroconductive material continuously or discretely by changing the relative positions of the opening of the shield and/or the anode electrode and the electroconductive material.
  • FIG. 15 is a schematic diagram illustrating the configuration of a surface treatment apparatus for an electroconductive material as an embodiment according to the present invention.
  • this apparatus 21 for treating the surface of an electroconductive material as an embodiment according to the present invention includes a modifying treatment cell 22, an electrolytic solution 23 stored in the modifying treatment cell 22, an anode electrode 24 and a cathode electrode 25 formed of an electroconductive target material that are immersed into the electrolytic solution 23 spaced apart from each other, and a direct current power supply 26 that is connected to the anode electrode 24 and the cathode electrode 25.
  • the modifying treatment cell 22 may be any known cell formed of a stable material.
  • the cell may be formed of, for example, glass, Teflon (registered trademark), or polyethyl ether ketone (PEEK).
  • the modifying treatment cell 22 may be a ceramic cell.
  • the surface treatment apparatus 21 illustrated in FIG. 16 described later can use even a metallic cell.
  • the electrolytic solution 23 is a solution that has electroconductivity and, when a voltage is applied between the anode electrode 24 and the cathode electrode 25 to form nano-level microstructures on the surface of the target material (the surface of the cathode electrode 25), hardly etches the surface of the target material excessively, adheres to or precipitates on the surface of the anode electrode 24 and the cathode electrode 25, and forms a sediment.
  • the electrolytic solution 23 may be an aqueous solution containing at least one type selected from the group consisting of potassium carbonate (K 2 CO 3 ), sodium carbonate (Na 2 CO 3 ), sodium hydrogencarbonate (NaHCO 3 ), ammonium carbonate ((NH 4 ) 2 CO 3 ), lithium hydroxide (LiOH), sodium hydroxide (NaOH), magnesium hydroxide (Mg(OH) 2 ), potassium hydroxide (KOH), ammonium hydroxide (NH 4 OH), sodium chloride (NaCl), potassium chloride (KCl), magnesium chloride (MgCl 2 ), ammonium chloride (NH 4 Cl), sulfates of lithium, sulfates of sodium, sulfates of magnesium, sulfates of potassium, sulfates of ammonium, nitrates of lithium, nitrates of sodium, nitrates of magnesium, nitrates of potassium, nitrates of ammonium, citrates of lithium, cit
  • the anode electrode 24 is an insoluble anode electrode formed of an electrode material that is not ionized and solved in the electrolytic solution 23 when a voltage is applied between the anode electrode 24 and the cathode electrode 25 to form nano-level microstructures on the target surface, thereby not precipitating on the cathode electrode 25 or hindering the formation of the nano-level microstructures.
  • Examples of the anode electrode 24 may include platinum (Pt) electrodes, palladium (Pd) electrodes, iridium (Ir) electrodes, and electrodes whose surface is coated with Pt, Pd, or Ir, and graphite electrodes.
  • the direct current power supply 26 applies a voltage of, for example, 60 V or more and 300 V or less between the anode electrode 24 and the cathode electrode 25.
  • the voltage is required for the modifying treatment on the surface of the cathode electrode 25 as the target material.
  • the direct current power supply 26 may be a known power supply.
  • the cathode electrode 25 is covered with the box 27, the anode electrode 24 is covered with the box 27 provided with the opening 28 as illustrated in FIG. 16 .
  • the surface of the cathode electrode 25 immersed into the electrolytic solution 23 may be covered with a insulating heat-resistant material such as a heat-resistant resin and glass, leaving the opening 28 for limiting the part to be treated of the cathode electrode 25.
  • the shape and size of the opening 28 are not limited, and the box 27 may be provided with a plurality of openings. In the case where a plurality of openings 28 are provided, the positions of the openings 28 are not limited in the same surface of the cathode electrode 25.
  • the openings 28 may be arranged on the front side and back side of the cathode electrode 25.
  • an inclined part 28a may be provided on the upper (liquid surface side) end of the opening 28. Providing the inclined part 28a allows gas generated from the part to be treated to efficiently escape to the electrolytic solution 23.
  • the surface treatment apparatus 21 having such a configuration manufactures a surface-modified electroconductive material as follows. Described below is a method for surface treatment of an electroconductive material using this surface treatment apparatus 21.
  • the box 27 is immersed into the electrolytic solution 23 stored in the modifying treatment cell 22, and then the anode electrode 24 and the cathode electrode 25 are immersed thereinto spaced apart from each other, whereby a system (a surface modifying treatment system) that performs a surface modifying treatment on the cathode electrode 25 is constructed.
  • a system a surface modifying treatment system
  • the cathode electrode 25 is immersed into the box 27, and a part desired to be treated is made visible through the opening 28 of the box 27.
  • the surface modifying treatment on the cathode electrode 25 is performed on a part exposed to the electrolytic solution 23 through the opening 28.
  • the anode electrode 24 is put into the box 27, and the box 27 is placed so that the opening 28 of the box 27 will face a part to be treated of the cathode electrode 25.
  • the part desired to be treated is spaced apart from the opening 28, the part desired to be treated becomes larger than the opening; because of this, the spacing (distance) between the opening 28 and the part desired to be treated of the cathode electrode 25 is generally preferably 5 mm or less and more preferably 1 mm or less.
  • the treated surface is observed with a SEM to check the following: protrusion structures having an average diameter of 1 ⁇ m or less are formed on the surface; the surface is not oxidized (except a natural oxide film with a thickness about a few nanometers); and the surface is not melted. Whether the surface is oxidized can be checked using the EDS in the SEM.
  • the surface modifying treatment system illustrated in FIG. 15 was constructed with a stainless steel sheet (SUS316) as the cathode electrode 25.
  • the dimensions of the opening 28 were set to be 25 mm ⁇ 4 mm.
  • a voltage was applied for 15 minutes with a 0.1 mol/L aqueous potassium carbonate (K 2 CO 3 ) solution as the electrolytic solution 23.
  • the surface of the stainless steel sheet after the treatment was observed with a SEM. The observation revealed that the lower limit voltage was 80 V. The upper voltage was found to be 250 V.
  • FIG. 19A, FIG. 19B , and FIG. 19C illustrate secondary electron images of the longitudinal (a) left part, (b) central part, and (c) right part of the opening 28, respectively, when 150 V was applied between the anode electrode 24 and the cathode electrode 25.
  • the microscopic protrusions are formed based on the occurrence of partial in-liquid plasma discharge in the vicinity of the cathode electrode 25.
  • the voltage applied between the anode electrode 24 and the cathode electrode 25 is less than the lower limit voltage, the partial in-liquid plasma discharge does not occur sufficiently and hence the microscopic protrusions are not formed.
  • the voltage applied between the anode electrode 24 and the cathode electrode 25 is the upper limit voltage or more, the occurrence of perfect plasma melts the surface of the cathode electrode 25, which is disadvantageous for the formation of the microscopic protrusions.
  • the in-liquid plasma discharge occurs as follows: When the temperature of the electrolytic solution 23 in the vicinity of the cathode electrode 25 locally reaches or exceeds its boiling temperature by application of a voltage and a gaseous phase is generated in the vicinity of the cathode electrode 25, the plasma discharge occurs in the gaseous phase.
  • the voltage application can be started at room temperature, it is more effective to perform the voltage application after setting the temperature of the entire electrolytic solution 23 or in the vicinity of the cathode electrode 25 is set to be within the range of from 80°C to 100°C. This is because the temperature in the vicinity of the cathode electrode 25 is effectively increased, whereby the in-liquid plasma discharge occurs efficiently.
  • a voltage application time can be any time, which is 1 second or more and 30 minutes or less, for example. Because a shorter voltage application time gives a smaller size of the formed microscopic protrusions, the voltage application time may be appropriately selected in accordance with desired surface shape and properties.
  • this method of surface treatment can manufacture an electroconductive material whose surface is formed with nano-level microstructures only by controlling the voltage applied between the anode electrode 24 and the cathode electrode 25 immersed into the electrolytic solution 23 at low cost and effectively without using expensive apparatuses and high-level techniques.
  • the electroconductive material whose surface is formed with nano-level microstructures can exhibit various functions caused by the microstructures.
  • the cathode electrode 25 or the box 27 By moving the cathode electrode 25 or the box 27 stepwise, or by moving them and discharging repeatedly, a discrete pattern can also be formed.
  • the cathode electrode 25 is not required to be covered with the box 27, and the surface treatment apparatus 21 can be expanded to continuous treatment equipment and a method of continuous treatment by forming the cathode electrode 25 to be a large-sized specimen or a band-shaped specimen.
  • Boxes 27 were manufactured from alumina plates having a thickness of 1.7 mm provided with various-sized openings (five types consisting of 5 mm ⁇ 5 mm, 5 mm in diameter, 10 mm in diameter, 10 mm ⁇ 2 mm, and 20 mm ⁇ 1 mm).
  • the upper end face of each opening 28 was formed inclined with an angle of 30 degrees as illustrated in FIG. 18 .
  • SUS316 stainless steel with a thickness of 1 mm as the cathode electrode 25 and Pt as the anode electrode 24 were immersed into an aqueous K 2 CO 3 solution with a concentration of 0.3 mol/L to construct the surface modifying treatment system as illustrated in FIG. 15 .
  • a voltage was applied between the cathode electrode 25 and the anode electrode 24.
  • FIG. 20 illustrates an example of the appearance of the cathode electrode 25 after being treated when the dimensions of the openings 28 were 5 mm ⁇ 5 mm and 5 mm in diameter.
  • the application voltage was 160 V, whereas the application time was 15 minutes.
  • FIG. 20 it has been found out that the surface of the cathode electrode 25 is treated in the shape of the opening 28.
  • FIG. 21 illustrates an example of a SEM image of the surface of the cathode electrode 25 after being treated when the dimension of the opening 28 was 5 mm in diameter.
  • FIG. 21 it has been found out that microscopic protrusion structures with a diameter of 1 ⁇ m or less, which are not present on a surface without any surface treatment performed (refer to FIG. 22 ), are formed on the surface of the cathode electrode 25.
  • the microscopic protrusion structures were formed with an application voltage of from 90 V to 200 V even when the opening 28 having another shape is used, but the number of the microscopic protrusion structures decreases with a voltage of 220 V or more. It is estimated that this is caused by the melting of the surface.
  • a stainless steel sheet (SUS316) was used as a cathode electrode, the anode electrode 24 was covered with the box 27 formed of alumina (thickness: 1.7 mm) provided with the opening 28 with dimensions of 1 mm (longitudinally) ⁇ 20 mm (laterally) to construct the surface modifying treatment system as illustrated in FIG. 16 .
  • the side having the opening 28 was placed spaced apart from the cathode electrode 25 by 1 mm.
  • the application voltages between the electrodes were 140 V and 220 V. The voltage was applied between the electrodes for 5 minutes, the stainless steel sheet was moved upward (vertically) by 5 mm, and then the voltage was applied thereto again for 5 minutes. The upward movement and the voltage application were repeated 10 times.
  • Two experiments were performed for the application voltages between the electrodes of 140 V and 220 V. Both experiments obtained a stainless steel sheet having areas in which microscopic protrusion structures exist at intervals of 5 mm.
  • a galvanized steel sheet was used as a cathode electrode, the anode electrode 24 was covered with the box 27 formed of alumina (thickness: 1.7 mm) provided with the opening 28 with dimensions of 1 mm (longitudinally) ⁇ 20 mm (laterally) to construct the surface modifying treatment system as illustrated in FIG. 16 .
  • the side provided with the opening 28 was placed spaced apart from the cathode electrode 25 by 1 mm.
  • the galvanized steel sheet was moved downward (vertically) by 20 mm with a velocity of 1 mm/minutes while applying the voltage between the electrodes, whereby a galvanized steel sheet having a treated area of 20 mm ⁇ 20 mm was prepared.
  • a methylene blue decolorization reaction test was performed on this surface, a remarkably higher photocatalytic effect was obtained than the surface without any surface treatment performed.
  • a commercial cold-rolled steel sheet with a thickness of 0.8 mm was cut to form cathode electrodes each having dimensions of 80 mm long and 6 mm wide.
  • the cathode electrodes each were bent in the width direction with the longitudinal direction as an axis so that the section in the width direction will have an arc shape with a radius of curvature of 10 mm.
  • a heat-resistant resin was applied onto the surfaces of the cathode electrodes 25 except connecting parts to the electrodes.
  • the openings 28 with a width of 2 mm and 4 mm and a length of 25 mm were formed on one side of each curved electrode.
  • a voltage of 150 V was applied between Pt and the cathode electrode 25.
  • microscopic protrusion structures having an average diameter of 1 ⁇ m or less were formed on the surfaces of the openings 28.
  • the present invention can provide a metallic material having new functions such as hydrophilic properties and luminescence properties.
  • the present invention can provide a method for surface treatment of a metallic material and a method for manufacturing a water-repellent material using a metallic material as a base that can impart high water-repellent properties to a metallic material surface without requiring much labor and cost.
  • the present invention can provide a surface treatment apparatus for and a method for surface treatment of an electroconductive material that can manufacture an electroconductive material formed with nano-level microstructures at low cost and efficiently by performing a treatment on a specific part in a surface or across a wide area in the surface.

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EP13752521.8A 2012-02-24 2013-02-21 Metallmaterial und oberflächenbehandlungsverfahren sowie vorrichtung Withdrawn EP2818579A4 (de)

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TWI472424B (zh) 2015-02-11
EP2818579A4 (de) 2015-11-11
JP5817907B2 (ja) 2015-11-18
TW201341176A (zh) 2013-10-16
KR20140112559A (ko) 2014-09-23
JPWO2013125658A1 (ja) 2015-07-30
WO2013125658A1 (ja) 2013-08-29
CN104114747A (zh) 2014-10-22
IN2014KN01697A (de) 2015-10-23

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