WO2013125658A1 - 金属材料、表面処理方法及び装置 - Google Patents

金属材料、表面処理方法及び装置 Download PDF

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Publication number
WO2013125658A1
WO2013125658A1 PCT/JP2013/054413 JP2013054413W WO2013125658A1 WO 2013125658 A1 WO2013125658 A1 WO 2013125658A1 JP 2013054413 W JP2013054413 W JP 2013054413W WO 2013125658 A1 WO2013125658 A1 WO 2013125658A1
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Prior art keywords
metal material
treated
cathode electrode
anode electrode
voltage
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PCT/JP2013/054413
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English (en)
French (fr)
Japanese (ja)
Inventor
名越　正泰
佐藤　馨
野呂　寿人
馬場　和彦
精一 渡辺
壮貴 吉田
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Ｊｆｅスチール株式会社
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Application filed by Ｊｆｅスチール株式会社 filed Critical Ｊｆｅスチール株式会社
Priority to IN1697KON2014 priority Critical patent/IN2014KN01697A/en
Priority to JP2014500933A priority patent/JP5817907B2/ja
Priority to CN201380009686.4A priority patent/CN104114747A/zh
Priority to EP13752521.8A priority patent/EP2818579A4/en
Priority to KR1020147022776A priority patent/KR101687462B1/ko
Publication of WO2013125658A1 publication Critical patent/WO2013125658A1/ja

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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 metal material, a surface treatment method for a metal material, a method for producing a water repellent material based on a metal material, a surface treatment apparatus for a conductive material, and a surface treatment method for a conductive material.
  • Non-Patent Document 1 there are a technique for forming a microstructure by anodizing a metal surface (see Non-Patent Document 1), a technique for forming a surface microstructure by electrolytic processing (see Non-Patent Document 2), and the like.
  • the metal material surface has the effect of improving workability by retaining oil and making the surface appearance uniform, but does not exhibit new functions.
  • a method for improving the paint adhesion of an automobile outer plate a method of forming phosphate crystals on the surface of a metal material has been proposed.
  • the particle diameter of phosphate crystals formed by this method has a size of several microns. For this reason, the metal material surface does not exhibit a new function.
  • a technique for forming a fine structure by anodizing a metal surface such as the technique described in Non-Patent Document 1
  • the surface becomes an oxide layer the surface physical properties are limited to the oxide species.
  • a method using electrolytic processing such as the method described in Non-Patent Document 2 requires a very short distance between the surface to be processed and the counter electrode in order to form a surface microstructure. Control is very difficult.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a metal material having new functions such as hydrophilic characteristics and light emission characteristics.
  • Another object of the present invention is to provide a surface treatment method for a metal material capable of imparting high water repellency to the surface of the metal material without much labor and cost, and a water repellency based on the metal material. It is to provide a method for manufacturing a material.
  • Another object of the present invention is to provide a conductive material that can be efficiently manufactured at a low cost by conducting a process over a predetermined area of the surface or a large area of the surface to form a nano-level microstructure.
  • the object is to provide a surface treatment apparatus and a surface treatment method.
  • the metal material according to the present invention includes a metal material substrate and a modified layer formed on the surface of the metal material substrate, and the modified layer is perpendicular to the surface of the metal material substrate.
  • the average diameter when viewed from any direction is 1 ⁇ m or less, and the projections protruding from the surface of the metal material substrate have an average of 3 or more within a range of 10 ⁇ m 2 .
  • the metal material according to the present invention is the metal material according to the above invention, wherein the modified layer includes a base portion protruding from a surface of the metal material base material, and a tip portion formed at an end portion of the base portion.
  • the average diameter when viewed from the direction perpendicular to the surface of the substrate is 1 ⁇ m or less, and the protrusions having a constricted structure whose outer diameter of the base portion is smaller than the outer diameter of the tip portion are averaged within a range of 10 ⁇ m 2. And one or more.
  • the metal material according to the present invention is characterized in that, in the above invention, the average diameter of the protrusion when viewed from a direction perpendicular to the surface of the metal material substrate is 500 nm or less.
  • the metal material according to the present invention is characterized in that, in the above-mentioned invention, the position where the protrusion is formed does not have periodicity in the in-plane direction of the metal material substrate.
  • the metal material according to the present invention is characterized in that, in the above-described invention, the modified layer includes a recess having an average diameter of 500 nm or less when viewed from a direction perpendicular to the surface of the metal material substrate.
  • the metal material according to the present invention is characterized in that, in the above-mentioned invention, the metal material substrate is made of alloy steel.
  • the metal material according to the present invention is characterized in that, in the above invention, the metal material base material is formed of a steel material.
  • the metal material according to the present invention is characterized in that, in the above invention, the composition of the metal material substrate and the composition of the protrusions are different.
  • the metal material according to the present invention is characterized in that, in the above-mentioned invention, the metal material substrate and the protrusion are continuously connected.
  • the surface treatment method for a metal material includes a step of immersing a material to be treated as a cathode electrode made of a metal material having a surface to be treated and an anode electrode in an electrolytic solution; Forming a microstructure on the surface to be treated by applying a voltage in a range where the material to be treated is not oxidized or melted at 70 V or higher between the electrode and the anode electrode; and from the electrolytic solution, the material to be treated And cleaning the material to be processed, and performing a water repellent treatment on the surface to be processed of the cleaned material to be processed.
  • the surface treatment method for a metal material according to the second aspect of the present invention includes a step of immersing a material to be treated as a cathode electrode made of a metal material having a surface to be treated and an anode electrode in an electrolytic solution; And applying a voltage of 70 V or more and 200 V or less between the anode electrode and the anode electrode, forming a microstructure on the surface to be processed, taking out the material to be processed from the electrolytic solution, And a step of performing a water repellent treatment on the treated surface of the treated material that has been washed.
  • the method for producing a water-repellent material based on a metal material comprises immersing a metal material, which is a material to be treated as a cathode electrode having a surface to be treated, and an anode electrode in an electrolytic solution, A step of forming a fine structure on the surface of the metal material as the material to be treated by applying a voltage of 70 V or more and 200 V or less between the cathode electrode and the anode electrode; and taking out the metal material from the electrolytic solution And cleaning the metal material, and performing a water repellent treatment on the surface to be processed of the cleaned metal material.
  • a surface treatment apparatus for a conductive material according to the present invention is interposed between an anode electrode and a cathode electrode made of a conductive material, which are immersed in an electrolytic solution so as to be separated from each other, and between the anode electrode and the cathode electrode, A shielding object having an opening for limiting a portion to be processed of the cathode electrode, and a power source for applying a voltage between the anode electrode and the cathode electrode.
  • the surface treatment apparatus for a conductive material according to the present invention is characterized in that, in the above-mentioned invention, a mechanism for changing a position of the opening and / or a relative position between the anode electrode and the cathode electrode is provided.
  • the surface treatment apparatus for conductive material according to the present invention is characterized in that, in the above invention, the power source applies a voltage of 60 V or more and 300 V or less between the anode electrode and the cathode electrode.
  • the surface treatment apparatus for a conductive material according to the present invention is characterized in that, in the above invention, the shield is an insulating heat-resistant material having the opening covered on the surface of the cathode electrode.
  • the surface treatment apparatus for a conductive material according to the present invention is characterized in that, in the above invention, the conductive material is a metal material.
  • the surface treatment method for a conductive material according to the present invention is characterized in that the surface of a conductive material is treated using the surface treatment apparatus for a conductive material according to the present invention.
  • the metal material according to the present invention can provide a metal material having new functions such as hydrophilic characteristics and light emission characteristics.
  • high water repellency can be imparted to the surface of the metal material without much labor and cost. it can.
  • a conductive material in which a nano-level microstructure is formed over a predetermined area of the surface or a large area of the surface is efficiently manufactured at low cost. can do.
  • FIG. 1A is a plan view showing a configuration of a metal material according to an embodiment of the present invention.
  • 1B is a cross-sectional view taken along line AA in FIG. 1A.
  • FIG. 2 is an SEM photograph showing an example of a protrusion formed on the surface of a cold-rolled steel sheet.
  • FIG. 3 is a schematic diagram for explaining a method of calculating the outer diameter of the protrusion.
  • FIG. 4 is a schematic diagram for explaining the constriction structure of the protrusion.
  • FIG. 5 is an SEM photograph showing an example of a protrusion having a constricted structure formed on a cold-rolled steel sheet.
  • FIG. 6 is a cross-sectional TEM photograph showing an example of a protrusion having a constricted structure formed on a cold-rolled steel sheet.
  • FIG. 7 is an SEM photograph showing an example of a recess formed on the surface of stainless steel.
  • FIG. 8 is an SEM photograph showing an example of a recess formed on the surface of stainless steel.
  • FIG. 9 is a cross-sectional TEM photograph showing an example of a protrusion having a composition different from that of the substrate.
  • FIG. 10 is a cross-sectional TEM photograph showing a state where protrusions are continuously formed on the cold-rolled steel sheet.
  • FIG. 11 is a flowchart showing a flow of surface treatment of a metal material according to an embodiment of the present invention.
  • FIG. 11 is a flowchart showing a flow of surface treatment of a metal material according to an embodiment of the present invention.
  • FIG. 12 is a schematic diagram showing a configuration example of an apparatus used in the metal material surface treatment method according to an embodiment of the present invention.
  • FIG. 13 is a SEM photograph showing the surface of the surface-treated SUS316L stainless steel.
  • FIG. 14 is a view of the state in which distilled water is dropped on the surface of the stainless steel surface shown in FIG.
  • FIG. 15 is a schematic diagram showing a configuration of a conductive material surface treatment apparatus according to an embodiment of the present invention.
  • FIG. 16 is a schematic view showing a modification of the surface treatment apparatus shown in FIG.
  • FIG. 17 is a schematic view showing a modification of the surface treatment apparatus shown in FIG.
  • FIG. 18 is a diagram illustrating a configuration of the opening.
  • FIG. 19A is a diagram showing a secondary electron image on the left side in the length direction of the opening when 150 V is applied between the anode electrode and the cathode electrode.
  • FIG. 19B is a diagram showing a secondary electron image of the central portion in the length direction of the opening when 150 V is applied between the anode electrode and the cathode electrode.
  • FIG. 19C is a diagram illustrating a secondary electron image on the right side in the length direction of the opening when 150 V is applied between the anode electrode and the cathode electrode.
  • FIG. 20 is a diagram showing the appearance of the cathode electrode after processing with the size of the opening being 5 mm ⁇ 5 mm and 5 mm ⁇ .
  • FIG. 21 is a diagram showing an SEM image of the surface of the cathode electrode after processing with the size of the opening being 5 mm ⁇ .
  • FIG. 22 is a view showing an SEM image of the surface of the cathode electrode not subjected to surface treatment.
  • ⁇ Metal material ⁇ 1A and 1B are a plan view and a cross-sectional view taken along line AA in FIG.
  • the metal material 1 which is one Embodiment of this invention is equipped with the base material 2 and the projection part 3 as a modified layer formed on the surface of the base material 2.
  • the base material 2 is formed of a metal material.
  • metal materials include alloy steels including stainless steel, steel materials such as cold-rolled steel sheets containing Fe and C and a trace amount of alloy elements of about 3% by mass or less as required, soft steel sheets, high tensile strength of 2 GPa class Examples include high strength steel plates and hot rolled steel plates.
  • the shape of the substrate 2 is not particularly limited, and a plate shape, a rod shape, a line shape, a pipe shape, or the like can be used.
  • the base material 2 may be obtained by welding a plurality of members.
  • board thickness is not limited and it can utilize from 100 micrometers or less metal foil to the thick steel plate of thickness 3mm or more.
  • the protrusion 3 is formed by a microstructure protruding from the surface of the substrate 2 having an average diameter R as viewed from a direction perpendicular to the surface of the substrate 2 of 1 ⁇ m, preferably 500 nm or less.
  • FIG. 2 is a scanning electron microscope (SEM) photograph showing an example of a protrusion formed on the surface of a cold-rolled steel sheet. In the figure, the protrusion 3 is shown by an arrow.
  • the protrusion 3 is formed by energizing at 135 V for 30 minutes in a K 2 CO 3 aqueous solution having a concentration of 0.3 mol / L using a cold-rolled steel plate and a platinum electrode as a cathode electrode and an anode electrode, respectively.
  • the average diameter R of the protrusion 3 when viewed from a direction perpendicular to the surface of the cold-rolled steel sheet is a circle C having the same area as the area surrounded by the outline of the protrusion 3. Is calculated by calculating the diameter R of the circle C.
  • the in-plane distribution of the protrusions 3 is not limited, it is advantageous in manufacturing that there is no particular periodicity.
  • an excessive process is required, which is disadvantageous in production.
  • the protrusion 3 has a structure in which the outer diameter Lrmin of the base 3a is smaller than the outer diameter Lrmax of the tip 3b, that is, a constricted structure, compared with a case without a constricted structure,
  • the specific surface area of the substrate 2 and the internal voids are apparently increased. Therefore, the hydrophilic property etc. which are affected by the specific surface area can be further improved.
  • the protrusion part 3 which has a constriction structure gives the chemical reaction on the surface and its promotion function to the surface of the base material 2, and improves adhesiveness with the thin film layer formed on the surface of the base material 2. Can be expected.
  • protrusions 3 having a constricted structure with an outer diameter Lrmin of the base portion 3a smaller than the outer diameter Lrmax of the distal end portion 3b on average within a range of 10 ⁇ m 2 . Since the hydrophilic property is higher as the specific surface area is larger, it is advantageous to reduce the protrusion size and increase the number of protrusions, and the surface area with a constricted protrusion structure increases the specific surface area, further improving the hydrophilic property. To do.
  • the projecting portion 3 having a constricted structure (1) A cross-sectional sample of the surface of a metal material is manufactured by FIB (Focused Ion Beam) method or the like, and the cross-sectional sample is observed with an SEM or a transmission electron microscope (TEM). It can be confirmed by a method, (2) a method in which a metal material is tilted and observed by SEM.
  • FIG. 5 is an SEM photograph showing an example of the protrusion 3 having a constricted structure formed on the cold-rolled steel sheet. This is an image taken by tilting the sample by 70 degrees.
  • FIG. 6 is a cross-sectional TEM photograph showing an example of a protrusion 3 having a constricted structure formed on a cold-rolled steel sheet.
  • the protrusion having a constricted structure has an outer diameter Lrmin of the base portion 3a of 90% or less of the size of the outer diameter Lrmax of the distal end portion 3b as shown in the following formula (1), preferably the following formula (2):
  • it means a structure in which the outer diameter Lrmin of the base portion 3a is 80% or less of the outer diameter Lrmax of the distal end portion 3b.
  • the value of Lrmin / Lrmax was 0.38
  • the value of Lrmin / Lrmax was 0.62.
  • the outer diameter Lrmin of the base portion 3a is the minimum outer diameter of the base portion 3a when the base portion 3a is viewed from a direction perpendicular to the surface of the metal material substrate, and the outer diameter Lrmax of the tip portion 3b is equal to that of the metal material substrate. It is the maximum outer diameter of the tip 3b when viewed from a direction perpendicular to the surface.
  • recesses having an average diameter of 1 ⁇ m or less, preferably 500 nm or less when viewed from a direction perpendicular to the surface of the base material 2 are desirably formed. . Since the surface area of the metal material can be increased by forming the recesses in addition to the protrusions 3, the light emission characteristics and the hydrophilic characteristics of the metal material surface can be further improved. In addition, the presence of the concave portions in addition to the convex portions allows more lubricating oil and functional liquid to be retained for a longer time, so that a new function can be imparted to the surface of the substrate 2.
  • FIGS. 7 and 8 are SEM photograph diagrams showing an example of a recess formed on the surface of stainless steel.
  • FIG. 7 shows a state in which the metal material is observed from directly above the surface of the metal material
  • FIG. 8 shows a state in which the metal material is observed by tilting the metal material by 60 degrees.
  • the recesses shown in FIGS. 7 and 8 are formed by energizing SUS430 stainless steel and platinum electrodes at 115 V for 30 minutes in a 0.1 mol / L aqueous K 2 CO 3 solution using a cathode electrode and an anode electrode, respectively. It is.
  • the arrow in the figure indicates a recess.
  • recesses having a size of about 200 nm to 500 nm are formed all over the stainless steel surface.
  • the substance forming the protruding portion 3 may have the same composition as the base material 2 or may have a different composition, and can be used properly according to the purpose.
  • FIG. 9 is a cross-sectional TEM photograph showing an example of the protrusion 3 having a composition different from the composition of the substrate 2.
  • the base material 2 is made of SUS316 stainless steel, but the Cr concentration in the protrusion 3 is smaller than the Cr concentration in the base material 2. According to such a structure, it is expected that the catalytic function of Ni can be utilized more effectively while utilizing the advantages of SUS316 stainless steel. As an example, there is a possibility that it can be used as it is as a steam reforming catalyst containing Ni as an active ingredient.
  • FIG. 10 is a cross-sectional TEM photograph showing a state where protrusions are continuously formed on the cold-rolled steel sheet.
  • the protrusion 3 was a single crystal and had almost the same crystal orientation as the substrate 2.
  • Such a continuous structure is stable against mechanical action and chemical action, and in addition to the protrusion 3 being difficult to fall off, it is also effective when it is not desired to use a different substance or different element for the protrusion 3. It is.
  • Such a continuous structure can be formed by using a steel material or metal having a low content of an easily oxidizable alloy element (for example, Cr) as the base material 2.
  • the metal material 1 having such a structure can be produced by utilizing discharge in an electrolytic solution. Specifically, a direct current voltage of about 60 to 140 V is applied to the electrode in the electrolytic solution using a material to be treated and an inert metal such as platinum as a cathode electrode and an anode electrode, respectively.
  • the range of the applied voltage varies depending on the material to be processed, but can be easily determined while confirming the surface structure of the material to be processed by SEM.
  • the average diameter of the protrusions can be controlled. Specifically, in the case of the same material, the average diameter of the protrusion can be increased as the applied voltage is increased, the treatment time is increased, and the position deeper from the electrolytic solution liquid surface.
  • the applied voltage reaches a value that results in a complete plasma state
  • the surface of iron or stainless steel is excessively melted or oxidized. It is difficult to form a fine protrusion structure.
  • a suitable condition can be determined by comparing the result of observing the treated surface with an SEM with the treated condition.
  • the protrusion structure in which Ni is concentrated and Cr is deficient as shown in FIG. 9 can be formed by setting the discharge voltage higher.
  • the “complete plasma state” refers to a state in which light emission mixed with orange or light emission mainly composed of orange covers the cathode electrode surface during discharge.
  • Example 1 A soft cold-rolled steel sheet (CRS, size 2 mm ⁇ 20 mm ⁇ 0.7 mm) and Pt were immersed in an aqueous solution of K 2 CO 3 with a concentration of 0.3 mol / L as a cathode electrode and an anode electrode, respectively, and different energizing voltages were applied to the cathode A sample was prepared by energizing the electrode and the anode electrode. And the surface of the soft cold-rolled steel plate after electricity supply was observed by SEM, and the average diameter and density of the projection part currently formed in the surface were evaluated.
  • Example 2 SUS316 stainless steel (size: 25 mm ⁇ 2.5 mm ⁇ 0.8 mm) and Pt were immersed in an aqueous solution of K 2 CO 3 with a concentration of 0.3 mol / L as a cathode electrode and an anode electrode, respectively, and different energization voltages were applied to the cathode electrode. A sample was prepared by energizing the anode electrode. And the surface of the SUS316 stainless steel after electricity supply was observed by SEM, and the average diameter and density of the projection part currently formed in the surface were evaluated similarly to Example 1. FIG.
  • the sample was cut out from the soft cold-rolled steel sheet at the portion where the depth from the liquid level was different. Observations were made. Moreover, the photoluminescence of the surface of SUS316 stainless steel after energization was measured. As an apparatus, FP6200 manufactured by JASCO Corporation was used, and measurement was performed at a start wavelength of 350 nm, an end wavelength of 600 nm, and an excitation wavelength of 435 nm.
  • the stainless steel surface having the protrusions according to the present invention is an untreated stainless steel surface having no protrusions (Experiment No. 2).
  • the emission characteristics increase as the size of the protrusions decreases, and particularly high emission characteristics are obtained when the average diameter of the protrusions is 500 nm or less. From this result, it is expected that the stainless steel having the protrusions according to the present invention can be used as a metal material of a display element or an element using light in the visible light region.
  • Example 3 SUS316 stainless steel (thickness 1 mm ⁇ width 2.5 mm ⁇ length 30 mm) was used. The surface was mirror-polished with Diamond Wrap ML-150P. The stainless steel and Pt were immersed in 300 cm 3 of a 0.1 mol / L K 2 CO 3 aqueous solution as a cathode electrode and an anode electrode, respectively, and the cathode and anode electrodes were energized for 15 minutes at different energizing voltages. Produced. After the experiment, the electrode (SUS316 stainless steel) was thoroughly rinsed with distilled water and then sufficiently dried to conduct contact angle measurement experiments on the surfaces of three portions at a depth of 30 mm, 28 mm, and 26 mm from the liquid surface.
  • the electrode SUS316 stainless steel
  • Distilled water (made by Wako Pure Chemical Industries, Ltd.) was dropped with a micropipette, and each water drop was photographed from the side with a camera (EOS Kiss X2 made by Canon).
  • the sample was sufficiently dried, and the average diameter and density of the protrusions formed on the surface were evaluated in the same manner as in Example 1. Further, in order to evaluate how much the surface area of the obtained sample is increased with respect to the smooth surface, the surface area of the sample when the surface area of the smooth surface is 1 is defined as the specific surface area, and the following assumption is made: Based on the calculation. That is, assuming that the hemispherical protrusions having the average diameter obtained above exist on the smooth surface at the density obtained above, the number of times of the increase relative to the smooth surface was calculated. The results are shown in Table 3 below. As shown in Table 3, in the examples within the scope of the present invention, the sample (experiment No.
  • Example 4 A soft cold-rolled steel sheet (size: 1.5 mm ⁇ 20 mm ⁇ 0.7 mm) and Pt were immersed in an aqueous solution of K 2 CO 3 having a concentration of 0.3 mol / L as a cathode electrode and an anode electrode, respectively, and a cathode with an energization voltage of 110V A sample was prepared by energizing the electrode and the anode electrode for 30 minutes. In this example, the width of the sample was set to 1.0 mm different from those in Examples 1 and 2 in order to concentrate the electric field. And after electricity supply, the contact angle of one place was measured by the method similar to Example 3 regarding the 15-mm depth part from the liquid level. The result was a contact angle of 45 °.
  • Example 2 A typical SEM photograph is shown in FIG. As a result of the evaluation, the average diameter of the protrusions as viewed from above was 350 nm. Further, the density of the protrusions having a constricted structure was evaluated. Density of projections having a constricted structure, counted the number of projections having a constricted configuration in the same parts as of the evaluation of the average diameter and density of the projections (range), similar to the density of the projections, per 10 [mu] m 2 The average number of was calculated. As a result, it was confirmed that there were three on average.
  • Example 5 A soft cold-rolled steel plate (size 1.5 mm ⁇ 20 mm ⁇ 0.7 mm) and Pt were immersed in an aqueous solution of K 2 CO 3 having a concentration of 0.3 mol / L as a cathode electrode and an anode electrode, respectively, and the cathode was set at an energizing voltage of 95V. A sample was prepared by energizing the electrode and the anode electrode for 10 minutes. And after electricity supply, the contact angle of one place was measured by the method similar to Example 3 regarding the 15-mm depth part from the liquid level. The result was a contact angle of 60 °.
  • Example 1 After measuring the contact angle, it was dried and the surface of the same part was observed by SEM, and the average diameter and density of the protrusions formed on the surface and the density of the protrusions having a constricted structure were evaluated in the same manner as in Example 1. did. As a result of the evaluation, it was confirmed that the average diameter of the protrusions as viewed from above was 350 nm, and an average of one protrusion having a constricted structure was present within 10 ⁇ m 2 .
  • Example 6 A 6 mass% C-2 mass% Si-2 mass% Cr steel was rolled and the Vickers strength of a cross section of 25 g was evaluated to be 900, confirming that it was a 2GPa class ultra high strength steel.
  • the steel material cut into a size of 1 mm ⁇ 20 mm ⁇ 0.7 mm and Pt were immersed in an aqueous solution of K 2 CO 3 with a concentration of 0.1 mol / L as a cathode electrode and an anode electrode, respectively, and the cathode voltage was set at 110V.
  • the anode electrode was energized for 30 minutes.
  • the surface of the soft cold-rolled steel sheet having a depth of 18 mm from the liquid surface was observed by SEM, and the average diameter of the protrusions formed on the surface and the density of the protrusions having a constricted structure were evaluated.
  • the average diameter of the protrusions seen from above was 400 nm, and two protrusions having a constricted structure exist on average within 10 ⁇ m 2 .
  • FIG. 11 is a flowchart showing a flow of surface treatment of a metal material according to an embodiment of the present invention.
  • FIG. 12 is a schematic diagram showing a configuration example of an apparatus used in the metal material surface treatment method according to an embodiment of the present invention.
  • a material to be treated as a cathode electrode which is a metal material
  • an anode electrode are immersed in an electrolytic solution, and the cathode electrode
  • a voltage between the anode electrode and the anode electrode a fine structure is formed on the surface of the material to be processed (step S1). Specifically, as shown in FIG.
  • the anode electrode 13 and the material to be processed 14 are immersed in the electrolytic solution 12 in the container 11, and the anode electrode 13 and the electrode 13 are connected from the power source 16 through a conductive wire 15 such as a copper wire.
  • a conductive wire 15 such as a copper wire.
  • the electrolytic solution 12 is not particularly limited, and has electrical conductivity.
  • the surface treatment of the material to be treated 14 is performed, the surface of the material to be treated 14 is excessively etched, or the anode electrode 13 and the material to be treated are treated. It is a solution that hardly adheres to or precipitates on the surface of the material 14 or forms a precipitate.
  • Examples of the electrolyte of the electrolytic solution 12 include potassium carbonate (K 2 CO 3 ), sodium carbonate (Na 2 CO 3 ), sodium hydrogen carbonate (NaHCO 3 ), ammonium carbonate ((NH 4 ) 2 CO 3 ), water Lithium oxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), ammonium hydroxide (NH 4 OH), sodium chloride (NaCl), potassium chloride (KCl), ammonium chloride (NH 4 Cl), sulfuric acid Such as sodium salt, sulfuric acid potassium salt, sulfuric acid ammonium salt, nitric acid sodium salt, nitric acid potassium salt, nitric acid ammonium salt, sodium citrate (NaH 2 (C 3 H 5 O (COO) 3 )) Sodium salt of acid, potassium salt of citric acid, ammonium salt of citric acid, nitric acid, hydrochloric acid, etc. It can be exemplified.
  • the electrolytic solution 12 can have any pH and concentration as long as the surface of the material to be treated 14 can be modified.
  • the concentration thereof is not particularly limited and can be 0.001 mol / L or more, more preferably 0.005 mol / L or more. This is because if the concentration of the electrolytic solution 12 is too low, it may be difficult to maintain a suitable discharge state when a voltage is applied between the anode electrode 13 and the workpiece 14.
  • the upper limit of the concentration of the electrolytic solution 12 is not particularly provided, but can be, for example, 0.5 mol / L or less.
  • the pH of the electrolytic solution 12 can be set to an arbitrary value as long as the electrode does not cause excessive corrosion or etching, and can be set to, for example, pH 10 to 12.
  • the anode electrode 13 is formed of a material that is thermally and chemically stable during discharge. Examples of such an anode electrode 13 include Pt, Ir, and graphite.
  • the material to be treated 14 is not particularly limited as long as it is a metal material, and a cold-rolled material, a hot-rolled material, a cast material, and a processed product thereof (including welding) can be used if it is a steel material.
  • the steel type is not particularly limited, and carbon steel, low alloy steel, stainless steel, or the like can be used. Also, plated steel sheets including electrogalvanized steel sheets can be used.
  • the shape of the to-be-processed material 14 is not specifically limited, A plate shape, linear shape, rod shape, a pipe shape, or a processed component can be utilized.
  • the to-be-processed material 14 needs to be immersed in the electrolyte solution 12, and needs to be deeper than 1 mm from a liquid level at least.
  • a range from a partial plasma state in which irregularities are formed on the surface of the material 14 to a complete plasma state can be used.
  • the applied voltage is preferably in the range of about 70 to 200 V, and more preferably in the range of 80 to 150 V, when the size of the workpiece 14 is 1 mm ⁇ 1 mm ⁇ 20 mm.
  • This voltage range is applicable to most steel materials including alloy steels such as stainless steel.
  • this voltage range changes depending on the type and arrangement of the material 14 to be processed, it is preferable to determine by observing the surface of the material 14 to be processed by changing the voltage condition with an SEM.
  • the discharge voltage is a voltage for forming fine protrusions on the surface of the steel material. If the voltage is lower than the lower limit voltage, fine protrusions are not formed on the surface. Therefore, it can be determined by confirming the presence or absence of the fine protrusions by SEM. If the upper limit is exceeded, the surface to be treated will melt. Therefore, the upper limit can be determined as the voltage at which the surface melts. However, it is more desirable not to oxidize the surface. In that case, the voltage at which the surface is oxidized can be easily determined by examining the SEM and an energy dispersive X-ray spectrometer (EDS) attached to the SEM.
  • EDS energy dispersive X-ray spectrometer
  • oxygen When oxygen is detected with the same X-ray intensity as the oxide of the material 14 to be processed, it can be determined that the surface is oxidized. Further, with respect to the X-ray intensity of oxygen normalized by the intensity of the Fe L-line of the oxide of the object to be treated 14 (for example, it means an oxide of Fe in cold-rolled steel sheet or low alloy steel) The X-ray intensity normalized by the Fe—L line intensity of oxygen at 1 is required to be 1/3 or less. The surface inspection is performed by changing the voltage and discharging for 30 minutes, taking out the material 14 to be processed, washing it with water, drying it, introducing it into the SEM, and observing it.
  • Discharge treatment time should be 3 seconds or more. However, the discharge treatment time may be as long as, for example, 60 minutes. However, if the discharge treatment time is too long, the material to be treated 14 may be worn out, so a treatment time of 30 minutes or longer is not preferable.
  • the most preferable condition is to select an applied voltage close to the upper limit of the preferable condition range.
  • FIG. 13 shows an example in which a SUS316L stainless steel plate having a thickness of 0.8 mm is processed.
  • This SUS316L stainless steel plate was cut to a width of 2 mm and a length of 30 mm, and was made conductive with a copper wire to form a cathode electrode.
  • the anode electrode used was a 50-cm long Pt wire bent so as not to contact each other and formed into a planar shape.
  • the connecting part between the SUS316L stainless steel plate and the copper wire was heat-pressed with a heat-resistant resin so that the copper wire did not touch the electrolytic solution, and the 20 mm long portion of the electrode was immersed in the electrolytic solution.
  • the electrolytic solution was an aqueous solution of K 2 CO 3 having a concentration of 0.1 mol / L, the voltage was set to 130V, and the electric discharge was performed for 10 minutes.
  • the material to be processed 14 is then taken out from the electrolytic solution 12 and the material to be processed 14 is cleaned (step S2).
  • a water repellent treatment is performed on the treated surface of the treated material 14 that has been cleaned (step 3).
  • the cleaning method is performed for the purpose of removing the electrolytic solution on the surface, and includes a method of immersing in pure water or spraying. In addition to pure water, a weak acid or an alkaline solution may be used as long as the fine structure on the surface is not broken. At that time, electrolysis can be applied. After washing, it may be dried, or depending on the subsequent water repellent treatment, it may proceed to the next step without being dried.
  • the water repellent treatment method a method of applying a water repellent spray, a method of adsorbing an organic substance having a water repellent function such as a fluorine-based resin in a liquid phase or a gas phase, and the like can be adopted.
  • nanopro component: fluorocarbon resin, silicon resin
  • Coronyl Co., Ltd. is sprayed on the surface of the material to be treated 14 and dried for 12 hours or more, so that the surface of the material to be treated 14 is subjected to water repellent treatment. did. Thereby, a series of surface treatments are completed.
  • FIG. 14 shows the result of observing the state in which distilled water was dropped from the sample surface shown in FIG.
  • the contact angle of water was measured to be 152 °, and it was confirmed that super water-repellency was realized.
  • the contact angle of water in the sample not subjected to the water repellent treatment was 51 °. Further, when the same water repellent treatment was performed on the material that was not subjected to plasma discharge in the solution, the contact angle of water was 125 °. Therefore, in order to obtain a super water-repellent surface, it was confirmed that both plasma discharge in solution and water-repellent treatment were necessary.
  • Example 1 A commercially available 0.8 mm thick stainless steel SUS316L steel sheet was cut into 2 mm width and 30 mm length and degreased by immersing in dilute hydrochloric acid, and then conducting through a copper wire to obtain a cathode electrode.
  • the anode electrode was formed by bending a 0.5 mm ⁇ Pt wire having a length of 50 cm so as not to contact each other and forming it into a planar shape.
  • the connecting portion between the cathode electrode and the copper wire was heat-pressed with a heat-resistant resin, so that the copper wire did not touch the electrolytic solution, and the 20 mm long portion of the electrode was immersed in the electrolytic solution.
  • the electrolytic solution was a K 2 CO 3 aqueous solution having a concentration of 0.1 mol / L, the applied voltage was set within the range of 60 to 180 V, the electric discharge was performed for 10 minutes, and after completion, the plate was washed with pure water and dried. Then, water repellent treatment was performed by spraying Nanopro manufactured by Coronyl on the surface of the material to be treated and drying for 12 hours or more, and the water wettability was investigated. Water wettability was obtained by dropping distilled water at 6 locations 1 ⁇ m at a regular interval onto the electrode surface using a micropipette and shooting from the side using Canon's digital camera EOS Kiss X2. The contact angle was measured from the photograph taken and evaluated by taking the average of 6 locations.
  • Table 4 shows the test results. As shown in Table 4, it was confirmed that all of the inventive examples exhibited a high contact angle compared to the untreated material. Particularly in Invention Examples 3, 4 and 5 where the applied voltage is in the range of 120 to 140V, super water repellency with a contact angle of 150 ° or more is realized, and in Invention Example 5 where the applied voltage is 140V, the most is 153.6 °. It was confirmed that a high contact angle was exhibited.
  • the inventors of the present invention consider that it is conventionally impossible to form a nano-level microstructure for the purpose of efficiently producing a conductive material having a nano-level microstructure formed on the surface at a low cost. Intensive research was conducted, including the examination of the possibility of using plasma discharge in liquid. As a result, the inventors of the present invention have found that a nano-level microstructure can be formed on the surface of the conductive material by partially causing plasma discharge in liquid using the conductive material as a cathode electrode. It was.
  • the inventors of the present invention have studied a method of forming a nano-level microstructure on a specific portion of the surface of the conductive material, and the treated portion of the conductive material is immersed in an electrolyte solution together with the anode electrode, It was found that a nano-level microstructure can be formed in a specific portion of the surface of the conductive material by installing a shield having an opening between the conductive material and the anode electrode. Furthermore, the inventors of the present invention can change the relative position between the opening of the shielding object and / or the anode electrode and the conductive material, so that the surface of the conductive material continuously or discretely has nano-level fineness. It has been found that a structure can be formed.
  • FIG. 15 is a schematic diagram showing a configuration of a surface treatment apparatus for conductive material according to an embodiment of the present invention.
  • the surface treatment apparatus 21 for a conductive material according to an embodiment of the present invention includes a modification treatment cell 22, an electrolytic solution 23 stored in the modification treatment cell 22, and an electrolytic solution 23.
  • an anode electrode 24 immersed in a space apart from each other, a cathode electrode 25 made of a conductive material to be processed, and an anode electrode 24 and a DC power source 26 connected to the cathode electrode 25.
  • the cathode electrode 25 is covered with a box 27 made of an insulating material, and the box 27 is formed with an opening 28 for limiting a portion to be processed of the cathode electrode 25.
  • the box 27 is arranged so that the upper part is higher than the liquid level of the electrolytic solution 23.
  • the upper part of the box 27 may be opened, or may have a lid with a hole through which a conducting wire connecting the cathode electrode 25 and the DC power source 26 is passed.
  • modification treatment cell 22 a known cell made of a material that is stable with respect to the electrolytic solution 23, for example, a cell made of glass, Teflon (registered trademark), or polyethyl ether ketone (PEEK) can be used.
  • a ceramic cell can also be used as the modification treatment cell 22.
  • a metallic cell can be used in the surface treatment apparatus 21 shown in FIG. 16 to be described later.
  • the electrolytic solution 23 has electrical conductivity, and a voltage is applied between the anode electrode 24 and the cathode electrode 25 to form a nano-level microstructure on the surface to be processed (the surface of the cathode electrode 25). Further, it is a solution that hardly etches the surface to be treated, adheres to or precipitates on the surfaces of the anode electrode 24 and the cathode electrode 25, or forms a precipitate.
  • Examples of the electrolytic solution 23 include potassium carbonate (K 2 CO 3 ), sodium carbonate (Na 2 CO 3 ), sodium hydrogen carbonate (NaHCO 3 ), ammonium carbonate ((NH 4 ) 2 CO 3 ), water Lithium oxide (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), lithium sulfate, sodium sulfate, magnesium sulfate, potassium sulfate, ammonium sulfate, lithium nitrate, sodium nitrate, Magnesium nitrate, potassium nitrate, ammonium nitrate, lithium Citrate um, citrate sodium, such as sodium citrate (NaH 2 (C 3 H 5 O (COO) 3)),
  • the electrolytic solution 23 can have any pH and concentration as long as the surface treatment of the cathode electrode 25 can be performed.
  • the concentration is particularly limited. It can be 0.001 mol / L or more, more preferably 0.005 mol / L or more without any problems. This is because if the concentration is too low, it may be difficult to maintain a suitable discharge state when a voltage is applied between the anode electrode 24 and the cathode electrode 25.
  • the upper limit of the concentration is not particularly provided, but can be set to 0.5 mol / L or less, for example.
  • the pH of the electrolytic solution 23 can be set to any value as long as the electrode is not excessively corroded or etched, for example, pH 5 to 12.
  • the anode electrode 24 is ionized and dissolved in the electrolytic solution 23 when a voltage is applied between the anode electrode 24 and the cathode electrode 25 to form a nano-level microstructure on the surface to be processed. It is an insoluble anode electrode made of an electrode material that is deposited on the surface and does not hinder the formation of a nano-level microstructure.
  • an anode electrode 24 for example, a platinum (Pt) electrode, a palladium (Pd) electrode, an iridium (Ir) electrode, an electrode whose surface is coated with Pt, Pd, or Ir, or a graphite electrode can be used.
  • the cathode electrode 25 is a material to be treated whose surface is modified by application of a voltage, and is made of a conductive material (conductive material) such as a metal material or an alloy material.
  • a conductive material such as a metal material or an alloy material.
  • Examples of the material to be processed that functions as the cathode electrode 25 include a carbon steel material, an alloy steel material, a stainless steel material, and a nickel material.
  • the shape of the cathode electrode 25 (material to be processed) is not particularly limited, and can be a component having a plate shape, a belt shape, or a conductive material portion.
  • the material to be treated can be used as the cathode electrode 25 after the surface is optionally mirror-polished with sandpaper or the like.
  • the DC power supply 26 applies a voltage required for the modification treatment of the surface of the cathode electrode 25 that is a material to be processed, for example, a voltage of 60 V or more and 300 V or less between the anode electrode 24 and the cathode electrode 25.
  • a known power source can be used as the DC power source 26.
  • the cathode electrode 25 is covered by the box 27.
  • the anode electrode 24 may be covered by the box 27 in which the opening 28 is formed.
  • the portion to be processed of the cathode electrode 25 is not limited by the box 27 having the opening 28, but as shown in FIG. 17, at least the surface of the cathode electrode 25 immersed in the electrolytic solution 23 is heat resistant resin, glass or the like.
  • the insulating portion may be covered with an insulating heat-resistant material, and an opening 28 for limiting a portion to be processed of the cathode electrode 25 may be formed in a part of the heat-resistant material.
  • the shape and size of the opening 28 are not particularly limited, and the box 27 may have a plurality of openings.
  • the openings 28 are not limited to the same surface of the cathode electrode 25.
  • the openings 28 may be provided on the front surface side and the back surface side of the cathode electrode 25.
  • an inclined portion 28 a may be provided at an upper end (liquid level side) end of the opening 28.
  • the surface treatment device 21 may have a heating means such as a heater for heating the electrolytic solution 23 or a thermometer for measuring the temperature of the electrolytic solution 23. Further, the angle at which the cathode electrode 25 is installed may be perpendicular to the liquid surface of the electrolytic solution 23, but is not limited thereto. Further, for the purpose of promoting plasma generation on the surface of the cathode electrode 25, a mechanism for supplying a gas such as hydrogen, argon, water vapor or the like to the surface of the cathode electrode 25 may be provided.
  • a heating means such as a heater for heating the electrolytic solution 23 or a thermometer for measuring the temperature of the electrolytic solution 23.
  • the angle at which the cathode electrode 25 is installed may be perpendicular to the liquid surface of the electrolytic solution 23, but is not limited thereto.
  • a mechanism for supplying a gas such as hydrogen, argon, water vapor or the like to the surface of the cathode electrode 25 may be provided.
  • the surface treatment apparatus 21 having such a configuration produces a surface-modified conductive material as follows.
  • a surface treatment method for a conductive material using the surface treatment apparatus 21 will be described.
  • the anode 27 is placed in the box 27, and the box 27 is installed so that the opening 28 of the box 27 faces the portion to be treated of the cathode electrode 25. Since the part to be processed becomes larger than the opening part as the part to be processed is separated from the opening part 28, the interval (distance) between the part to be processed between the opening part 28 and the cathode electrode 25 is usually preferably 5 mm or less. 1 mm or less is more preferable.
  • a predetermined voltage is applied between the anode electrode 24 and the cathode electrode 25 to modify the surface of the cathode electrode 25 (surface modification treatment step).
  • the predetermined voltage is a voltage that can be determined in a preliminary experiment, and can be determined by the following method. That is, first, the voltage applied to the surface modification treatment system and the treatment time are changed within a desired range. If the processing time is not specified, it may be performed for 15 minutes. The range in which the voltage is changed may be about 50 to 300V.
  • the treated surface is observed with an SEM, and a protrusion structure having an average of 1 ⁇ m or less is formed on the surface, the surface is not oxidized (excluding a natural oxide layer having a thickness of several nanometers), Confirm that it has not been melted, and determine the conditions. Whether or not the surface is oxidized can be confirmed by using EDS in the SEM.
  • the voltage range varies somewhat depending on the type of the cathode electrode 25, but is in the range of 60V to 300V, preferably in the range of 80 to 180V.
  • the lower limit voltage corresponds to the voltage at which plasma is generated.
  • the upper limit voltage is determined by oxidation of the surface due to high temperature or melting of the surface and disappearing of the fine protrusion structure. Although a preferable voltage range can be determined as described above, a higher applied voltage may be set when it is desired to process for a short time or to increase the protrusion structure.
  • the surface modification treatment system shown in FIG. 15 was constructed using a stainless steel plate (SUS316) as the cathode electrode 25.
  • the size of the opening 28 was set to 25 mm ⁇ 4 mm.
  • a 0.1 mol / L potassium carbonate (K 2 CO 3 ) aqueous solution was energized as an electrolytic solution 23 for 15 minutes.
  • the lower limit voltage was found to be 80V.
  • an upper limit voltage is 250V.
  • the fine protrusions are formed due to partial plasma discharge in liquid near the cathode electrode 25. That is, in this method, if the voltage applied between the anode electrode 24 and the cathode electrode 25 is less than the lower limit voltage, the partial plasma discharge in the liquid does not sufficiently occur and fine protrusions are not formed, and the voltage is higher than the upper limit voltage. Then, the generation of complete plasma melts the surface of the cathode electrode 25, which is disadvantageous for the formation of fine protrusions.
  • plasma discharge occurs in the gas phase when the temperature of the electrolytic solution 23 in the vicinity of the cathode electrode 25 locally exceeds the boiling point due to application of a voltage and a gas phase is generated in the vicinity of the cathode electrode 25. This is thought to be caused by the occurrence of For this reason, it is possible to apply a voltage from room temperature, but it is more effective if the temperature of the entire electrolytic solution 23 or the vicinity of the cathode electrode 25 is set in the range of 80 ° C. to 100 ° C. This is because the temperature in the vicinity of the cathode electrode 25 can be efficiently raised to efficiently cause plasma discharge in liquid.
  • the voltage application time can be any time, for example, 1 second or more and 30 minutes or less. The shorter the voltage application time, the smaller the size of the fine protrusions to be formed. Therefore, the voltage application time may be appropriately selected according to the desired surface shape and characteristics.
  • the voltage applied between the anode electrode 24 and the cathode electrode 25 immersed in the electrolytic solution 23 without using an expensive apparatus and advanced technology. It is possible to efficiently produce a conductive material having a nano-level microstructure formed on the surface at low cost simply by controlling the above.
  • a conductive material having a nano-level microstructure formed on the surface can exhibit various functions due to the microstructure. Surface modification can be performed for a wider area of the cathode electrode 25 by moving the cathode electrode 25 with the box 27 fixed or by moving the box 27 with the cathode electrode 25 fixed. Moreover, a continuous processing surface is obtained by moving continuously while processing.
  • Example 1 Boxes 27 having various sizes of openings (5 mm ⁇ 5 mm, 5 mm ⁇ , 10 mm ⁇ , 10 mm ⁇ 2 mm, and 20 mm ⁇ 1 mm) on an alumina plate having a thickness of 1.7 mm were produced.
  • the upper end surface of the opening 28 was processed obliquely by 30 degrees as shown in FIG.
  • a SUS316 stainless steel with a thickness of 1 mm is used as the cathode electrode 25, and Pt is immersed in a 0.3 mol / L K 2 CO 3 aqueous solution as the anode electrode 24 to construct a surface modification treatment system as shown in FIG. did.
  • a voltage was applied between the cathode electrode 25 and the anode electrode 24.
  • FIG. 20 shows an example of an external appearance photograph of the cathode electrode 25 after processing with the size of the opening 28 being 5 mm ⁇ 5 mm and 5 mm ⁇ .
  • the applied voltage is 160 V and the application time is 15 minutes.
  • FIG. 20 it was confirmed that the surface of the cathode electrode 25 was processed into the shape of the opening 28.
  • FIG. 21 shows an example of an SEM image of the surface of the cathode electrode 25 after processing the size of the opening 28 to 5 mm ⁇ .
  • a fine protrusion structure having a diameter of 1 ⁇ m or less that was not formed on the surface that was not subjected to the surface treatment was formed on the surface of the cathode electrode 25.
  • the fine protrusion structure could be formed with an applied voltage of 90 to 200V even when other shapes of the opening 28 were used, but the fine protrusion structure decreased at 220V or more. This is presumed to be due to surface melting.
  • a uniform water repellent treatment was performed on the entire surface of the cathode electrode 25 shown in FIG.
  • Example 2 A stainless steel plate (SUS316) is used as a cathode electrode, and the anode electrode 24 is covered with a box 27 made of alumina (thickness 1.7 mm) provided with an opening 28 of 1 mm (longitudinal direction) ⁇ 20 mm (lateral direction).
  • a surface modification system as shown was constructed. The surface with the opening 28 was placed 1 mm away from the cathode electrode 25.
  • the applied voltage between the electrodes was 140V and 220V.
  • a voltage was applied between the electrodes for 5 minutes, then the stainless steel plate was moved 5 mm upward (longitudinal direction), and the voltage was applied again for 5 minutes.
  • the upward movement and voltage application were repeated 10 times.
  • Two kinds of experiments were conducted, in which the applied voltage between the electrodes was 140V and 220V. As a result, it was possible to obtain a stainless steel plate having a region where a fine projection structure exists at intervals of 5 mm.
  • Example 3 The anode electrode 24 is covered with a box 27 made of alumina (thickness 1.7 mm) provided with an opening 28 of 1 mm (longitudinal direction) ⁇ 20 mm (lateral direction) using a Zn-plated steel plate as a cathode electrode, as shown in FIG.
  • a simple surface modification treatment system was constructed. The surface with the opening 28 was placed 1 mm away from the cathode electrode 25. The applied voltage between the electrodes was 120 V, and the Zn-plated steel sheet was moved 20 mm downward (longitudinal direction) at a speed of 1 mm / min while applying a voltage between the electrodes. A Zn-plated steel sheet with a treated area of 20 mm ⁇ 20 mm could be produced.
  • this surface was subjected to a methylene blue decolorization reaction test, a significantly higher photocatalytic effect was obtained as compared with the surface not subjected to surface treatment.
  • Example 4 A commercially available cold-rolled steel sheet having a thickness of 0.8 mm was cut into a length of 80 mm and a width of 6 mm to obtain a cathode electrode. Bending was performed in the width direction so that the length direction was an axis, and the cross-section in the width direction was processed into an arc shape with a local radius of 10 mm. A heat-resistant resin was applied to the surface of the cathode electrode 25 except for the connection portion with the electrode, and an opening 28 having a width of 2 mm and a width of 4 mm and a length of 25 mm was formed on one curved surface. A voltage of 150 V was applied between the cathode electrode 25 of Pt. In both samples, a fine protrusion structure having an average diameter of 1 ⁇ m or less was formed on the surface of the opening 28.
  • a surface treatment method for a metal material capable of imparting high water repellency to the surface of the metal material without much labor and cost, and a method for producing a water repellent material based on the metal material can be provided.
  • a surface treatment apparatus for a conductive material capable of efficiently producing a conductive material formed with a nano-level fine structure by performing treatment over a predetermined place on the surface or a large area of the surface, and A surface treatment method can be provided.

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06297252A (ja) * 1993-04-09 1994-10-25 Sony Corp 微細加工方法及びその装置
JPH09241865A (ja) * 1996-03-01 1997-09-16 Kawasaki Steel Corp フィルム密着性、耐食性に優れたラミネート鋼板
JP2004521186A (ja) * 2000-08-10 2004-07-15 ナトゥール・インコーポレイテッド 外的影響を用いて加工物の頂部表面とキャビティ表面上に付着する添加物の間に差を作り出すめっき方法および装置
JP2008285754A (ja) * 2001-03-14 2008-11-27 Nikko Kinzoku Kk パーティクル発生の少ないスパッタリングターゲット、バッキングプレート又はスパッタリング装置内の機器及び粗化方法
JP2010287648A (ja) * 2009-06-10 2010-12-24 Seiko Epson Corp 半導体装置の製造方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59227241A (ja) * 1983-06-09 1984-12-20 Taishi Shokuhin Kogyo Kk 乳酸発酵豆乳の製造法
JPH04136198A (ja) * 1990-09-26 1992-05-11 Nau Chem:Yugen 電気めっき方法
AUPR129900A0 (en) * 2000-11-08 2000-11-30 Chang, Chak Man Thomas Plasma electroplating
JP2005329451A (ja) * 2004-05-21 2005-12-02 Fuji Photo Film Co Ltd アルミニウム板の表面加工方法及び平版印刷版用支持体並びに平版印刷版
JP5010966B2 (ja) * 2006-08-21 2012-08-29 株式会社神戸製鋼所 撥水性塗料および撥水金属板
EP2112670B1 (en) * 2007-02-15 2018-04-18 Kankyou Engineering Co., Ltd. Method for producing conductor fine particles
EP2133448B1 (en) * 2007-03-02 2019-10-30 Furukawa Electric Co., Ltd. Production method and device for surface roughening of a copper plate
JP5569259B2 (ja) * 2010-08-26 2014-08-13 Ｊｆｅスチール株式会社 表面改質された導電性材料の製造方法
CN102041540A (zh) * 2011-01-13 2011-05-04 中国科学院苏州纳米技术与纳米仿生研究所 三维渐变孔阵列纳米结构阳极氧化铝模板及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06297252A (ja) * 1993-04-09 1994-10-25 Sony Corp 微細加工方法及びその装置
JPH09241865A (ja) * 1996-03-01 1997-09-16 Kawasaki Steel Corp フィルム密着性、耐食性に優れたラミネート鋼板
JP2004521186A (ja) * 2000-08-10 2004-07-15 ナトゥール・インコーポレイテッド 外的影響を用いて加工物の頂部表面とキャビティ表面上に付着する添加物の間に差を作り出すめっき方法および装置
JP2008285754A (ja) * 2001-03-14 2008-11-27 Nikko Kinzoku Kk パーティクル発生の少ないスパッタリングターゲット、バッキングプレート又はスパッタリング装置内の機器及び粗化方法
JP2010287648A (ja) * 2009-06-10 2010-12-24 Seiko Epson Corp 半導体装置の製造方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HIDEAKI TAKAHASHI; MASATOSHI SAKAIRI; TATSUYA KIKUCHI; HIMENDRA JHA, HYOMEN GIJUTSU, vol. 60, no. 3, 2009, pages 14
See also references of EP2818579A4 *
WATARU NATSU: "Application and Theory of Micro Electrochemical Machining", HYOMEN GIJUTSU, vol. 61, 2010, pages 294

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TWI472424B (zh) 2015-02-11
EP2818579A4 (en) 2015-11-11
EP2818579A1 (en) 2014-12-31
KR20140112559A (ko) 2014-09-23
KR101687462B1 (ko) 2016-12-16
CN104114747A (zh) 2014-10-22
JP5817907B2 (ja) 2015-11-18
JPWO2013125658A1 (ja) 2015-07-30
TW201341176A (zh) 2013-10-16

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