WO2012026624A1 - 表面改質された導電性材料の製造方法 - Google Patents
表面改質された導電性材料の製造方法 Download PDFInfo
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- WO2012026624A1 WO2012026624A1 PCT/JP2011/069974 JP2011069974W WO2012026624A1 WO 2012026624 A1 WO2012026624 A1 WO 2012026624A1 JP 2011069974 W JP2011069974 W JP 2011069974W WO 2012026624 A1 WO2012026624 A1 WO 2012026624A1
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
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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
- C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Definitions
- the present invention relates to a method for producing a surface-modified conductive material, and more particularly, to a method for producing a conductive material having a nano-level microstructure formed on the surface.
- a method of forming a nano-level microstructure on the surface of a material there is a method of forming a nanometer-sized microstructure on the surface of a substrate or the like using a photolithographic method or a chemical vapor deposition method (CVD).
- CVD chemical vapor deposition method
- Patent Document 1 a high voltage is applied between a cathode and an anode placed in an electrolytic solution to cause glow discharge in the vicinity of the cathode to generate plasma (hereinafter referred to as “liquid plasma discharge”).
- liquid plasma discharge a method of locally melting the cathode material and forming conductive fine particles (nanoparticles) made of the cathode material in a solution.
- the voltage in order to form a small particle, the voltage (it depends on the kind of cathode material to be used etc., for example, high voltage of 140-300V) which exhibits the complete plasma state which plasma luminescence produces from the electrode whole surface is applied. This is applied to generate plasma discharge in liquid.
- Patent Documents 2 and 3 a material to be treated as a cathode and an anode provided with one or more openings are installed, and an electrolytic solution that has flowed through the opening of the anode is placed on the surface of the material to be treated.
- a method is proposed in which the surface of the material to be treated is washed by applying a predetermined voltage between the material to be treated (cathode) and the anode, or the surface of the material to be treated is washed and then coated. Has been.
- Patent Documents 1 to 3 are techniques for producing nanoparticles from a cathode material or cleaning the surface of a material to be treated, and have a nano-level microstructure on the surface of the cathode material. There is no technical idea of forming, and discharge is performed under conditions where the surface roughness of the cathode material (material to be treated) is large, so a nano-level microstructure is formed on the surface of the cathode material itself. could not be used to do.
- an object of the present invention is to provide a method capable of efficiently producing a conductive material having a nano-level microstructure formed on the surface at low cost.
- the present inventors In order to efficiently produce a conductive material having a nano-level microstructure formed on the surface at a low cost, the present inventors have conventionally considered that it is impossible to form a nano-level microstructure. Intensive research was conducted, including the study of the possibility of using plasma discharge in liquid. Then, the present inventors use the material to be treated as a cathode electrode to cause partial plasma discharge in liquid within a predetermined voltage range, thereby forming a nano-level microstructure on the surface of the material to be treated (cathode electrode). The present invention has been completed.
- the object of the present invention is to advantageously solve the above-mentioned problems.
- the method for producing a surface-modified conductive material according to the present invention comprises an insoluble anode electrode, an object to be treated, and an electrolytic solution.
- a first material between the insoluble anode electrode immersed in the electrolytic solution and the material to be treated as the cathode electrode is immersed in the material to be treated as a cathode electrode made of a conductive material having a surface.
- a surface modification treatment step of modifying the surface to be treated by applying a voltage higher than or equal to a voltage and less than a second voltage, wherein the first voltage is a positive voltage in the voltage-current characteristics of the surface modification treatment system.
- a current value 1 ⁇ 2 of the sum of the first current maximum value first appearing in the region and the first current minimum value first appearing in the positive voltage region (that is, the first current maximum value and the first current minimum value) Intermediate voltage), and the second voltage is completely plasma. Characterized in that it is a voltage exhibiting.
- the “electrolytic solution” has electrical conductivity, has a higher ionization tendency than the material to be treated, and excessively etches the surface to be treated when modifying the surface to be treated.
- the components in the solution may be deposited on the non-treated surface or precipitates may be formed, thereby substantially hindering the desired modification treatment of the surface to be treated (ie, formation of nano-level microstructure).
- metal ions may be present in the electrolytic solution as long as they are metal ions that are deposited on the surface of the cathode electrode during the modification treatment (electrolysis) and do not hinder the formation of the nano-level microstructure.
- the “insoluble anode electrode” refers to an electrode made of a conductive material that is not substantially ionized in an electrolytic solution when the surface to be treated is modified.
- the “surface modification treatment system” refers to a system that includes an insoluble anode electrode, a cathode electrode (material to be treated), and an electrolytic solution, and performs surface modification treatment on the material to be treated.
- the ⁇ voltage-current characteristics of the treatment system '' can be obtained by measuring the change in the current value when the voltage applied between the insoluble anode electrode and the cathode electrode immersed in the electrolytic solution is continuously changed. it can.
- the “complete plasma state” refers to a state in which light emission mixed with orange or light mainly composed of orange covers the cathode electrode surface during discharge.
- Voltage exhibiting a complete plasma state is a value obtained when a voltage is applied for 30 minutes in steel materials including carbon steel and alloy steel, stainless steel, and materials that are oxidized at high temperature by atmospheric heating such as Zn and Al. It can be defined as the voltage at which the surface layer of the electrode is oxidized with a thickness of at least 100 nm.
- the oxidized thickness of the surface layer of the cathode electrode can be determined by observing the cross section of the cathode electrode with an SEM and measuring the average thickness of the oxidized layer.
- the oxide layer can be clearly distinguished from the ground by the reflected electron image of the SEM, and the average thickness of the oxide layer is the thickness of the oxide layer with respect to a cross section having a length of 10 ⁇ m parallel to the surface of the cathode electrode. It can be evaluated by taking the average value.
- the oxidized thickness includes the void or the like.
- the method for producing a surface-modified conductive material of the present invention it is preferable to apply a voltage of 60 V or more and less than 140 V between the insoluble anode electrode and the cathode electrode. If the applied voltage is 60 V or more, a nano-level fine structure can be formed on the surface to be processed, and surface modification can be sufficiently achieved. If the applied voltage is less than 140 V, complete plasma is generated. This is because it can be sufficiently suppressed to prevent a nano-level microstructure from being formed on the surface to be processed due to oxidation of the material to be processed.
- the conductive material is preferably a metal or an alloy material.
- Metal materials and alloy materials are relatively inexpensive compared to semiconductor materials and the like, and are easy to process and mold among conductive materials. Therefore, conductive materials that are surface-modified according to the method of the present invention. This is because it is particularly suitable.
- the conductive material is preferably a steel material containing carbon (hereinafter referred to as “carbon steel material”).
- Carbon steel is relatively suitable as a conductive material that is surface-modified according to the method of the present invention, because it is relatively inexpensive compared to semiconductor materials and is easy to process and mold among conductive materials. Because.
- the conductive material is preferably a stainless steel material.
- Stainless steel is relatively inexpensive compared to semiconductor materials, is easy to process and mold among conductive materials, and has high corrosion resistance. This is because it is particularly suitable as a material.
- the electrolytic solution comprises potassium carbonate, sodium carbonate, sodium bicarbonate and ammonium carbonate, lithium hydroxide, sodium hydroxide, magnesium hydroxide, hydroxide Sulfates such as potassium and ammonium hydroxide, sodium chloride, potassium chloride, magnesium chloride and ammonium chloride, lithium, sodium, magnesium, potassium and ammonium, nitrates such as lithium, sodium, magnesium, potassium and ammonium, lithium, sodium, magnesium , Citrates such as potassium and ammonium, and an aqueous solution containing at least one selected from the group consisting of sulfuric acid, nitric acid, hydrochloric acid and citric acid.
- a conductive material having a nano-level microstructure formed on the surface can be efficiently manufactured at low cost.
- TEM transmission electron microscope
- an insoluble anode electrode and a material to be treated as a cathode electrode made of a conductive material are immersed in an electrolytic solution, and then the insoluble anode electrode and the cathode are immersed.
- a voltage within a specified range to the electrode the material to be processed made of a conductive material
- a nano-level microstructure is formed on the surface of the material to be processed (surface to be processed), and the surface is modified. It is characterized by manufacturing a conductive material.
- an example of the method for producing a surface-modified conductive material of the present invention is not particularly limited, and can be carried out using a surface modification apparatus 1 as shown in FIG. 1, for example.
- a surface modification apparatus 1 shown in FIG. 1 includes a modification treatment cell 2, an electrolytic solution 3 stored in the modification treatment cell 2, an anode electrode 4 immersed in the electrolytic solution 3 at a distance from each other, and a conductive layer.
- the liquid surface of the electrolytic solution 3 in the reforming treatment cell 2 may be optionally covered with a heat resistant resin (not shown).
- the surface modification device 1 may include a heating means (not shown) such as a heater for heating the electrolytic solution 3.
- the modification treatment cell 2 a known cell made of a material that is stable with respect to the electrolytic solution 3, for example, a cell made of glass, Teflon (registered trademark), or polyethyl ether ketone (PEEK) can be used.
- a cell made of glass, Teflon (registered trademark), or polyethyl ether ketone (PEEK) can be used.
- the electrolytic solution 3 has electrical conductivity, has a higher ionization tendency than the material to be processed as the cathode electrode 5, and applies a voltage between the anode electrode 4 and the cathode electrode 5 (material to be processed).
- a nano-level microstructure is formed on the surface to be processed (the surface of the cathode electrode 5)
- the surface to be processed is excessively etched, adhered to or deposited on the surfaces of the anode electrode 4 and the cathode electrode 5, and precipitates. It is a solution that is difficult to form.
- Examples of the electrolytic solution 3 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 ), hydroxide Lithium (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, citrate sodium, such as sodium citrate (NaH 2 (C 3 H 5 O (COO) 3), citrate
- the electrolytic solution 3 can have any pH and concentration as long as the surface modification of the conductive material that is the material to be treated can be performed.
- 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 is too low, it may be difficult to maintain a suitable discharge state when a voltage is applied between the anode electrode 4 and the cathode electrode 5.
- concentration is not provided in particular, it can be 0.5 mol / L or less, for example.
- the pH of the electrolytic solution 3 can be set to an arbitrary value as long as the electrode is not excessively corroded or etched. For example, the pH can be set to 5 to 12.
- the liquid surface of the electrolytic solution 3 in the reforming treatment cell 2 is It can also be covered with a heat-resistant resin such as a fluororesin heat-shrinkable tube.
- the electrolytic solution 3 is an insoluble anode electrode made of an electrode material which is ionized and dissolved in 3 and deposited on the cathode electrode 5 and does not hinder the formation of a nano-level microstructure.
- anode electrode 4 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, a graphite electrode, or the like can be used.
- the cathode electrode 5 is a material to be treated whose surface is modified by applying 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 treated (conductive material) functioning as the cathode electrode 5 include carbon steel materials, alloy steel materials, stainless steel materials, nickel materials, and the like.
- the shape of the cathode electrode 5 (material to be processed) is not particularly limited, and may be a plate shape, a wire (wire) shape, or a strip shape.
- the material to be treated (conductive material) can be optionally used as the cathode electrode 5 after mirror-polishing the surface with sandpaper or the like.
- the direct current power source 6 applies a voltage required for the modification treatment of the surface of the cathode electrode 5 which is a material to be treated, for example, a voltage of 60 V or more and less than 140 V between the anode electrode 4 and the cathode electrode 5.
- a known power source can be used as the DC power source 6.
- the surface-modified conductive material is manufactured, for example, as follows according to the method for manufacturing the surface-modified conductive material of the present invention. Can do.
- an anode electrode 4 that is an insoluble anode electrode and a cathode electrode 5 that is a material to be treated made of a conductive material are immersed in an electrolytic solution 3 stored in the reforming treatment cell 2 so as to be separated.
- a system (surface modification treatment system) for performing a surface modification treatment of the treatment material is constructed.
- the surface modification treatment of the material to be treated (cathode electrode 5) occurs in the portion immersed in the electrolytic solution 3.
- a voltage V (0 ⁇ V 1 ⁇ V ⁇ V 2 ) that is equal to or higher than a predetermined first voltage V 1 and lower than a predetermined second voltage V 2 is applied between the anode electrode 4 and the cathode electrode 5. Then, the surface of the material to be treated (cathode electrode 5) is modified (surface modification treatment step).
- the first voltage V 1 the voltage of the surface modification treatment system that has been previously measured - a voltage can be determined from the current characteristic.
- the first voltage V 1 is the maximum value (V) that the gradually increased current I takes when the applied voltage V is increased in the voltage-current characteristics of the surface modification treatment system.
- the first current maximum value I MAX that is the first maximum current I that appears in the positive voltage region of> 0) and the current I that gradually decreased after taking the first current maximum value I MAX before increasing again.
- the first voltage V 1 is, for example, the following procedures (1) to (3):
- the voltage-current characteristics As the voltage-current characteristics. 2 shows voltage-current characteristics of a surface modification treatment system using a cold-rolled steel sheet as a material to be treated, and FIGS. 3A and 3B show a surface modification treatment system using a stainless steel material as a material to be treated.
- FIG. 4 shows the voltage-current characteristics of the surface modification treatment system using nickel as the material to be treated.
- the second voltage V 2 is a voltage causing a complete plasma state.
- the second voltage V 2 is, for example, repeated by applying a voltage for 30 minutes while increasing the voltage applied to the surface modification treatment system stepwise by 5 V or 10 V, and the surface layer of the cathode electrode has a thickness of at least 100 nm.
- the voltage to be oxidized can be determined experimentally.
- the magnitudes of the first voltage V 1 and the second voltage V 2 differ depending on the surface modification processing system.
- the magnitude of the first voltage V 1 is often 60 V or more
- the second voltage V 2 The size of is often 140 V or less.
- the first voltages V 1 is 80V
- the second voltage V 2 is 140 V.
- the conductive material is stainless steel (SUS316L)
- the first voltages V 1 is 55V
- the second voltage V 2 is 125V.
- the first voltages V 1 or more by applying a second voltage V 2 less than the voltage V, the surface of the cathode electrode 5 to be processed material
- a large number of fine protrusions having a height and a diameter of nano size, preferably 500 nm or less, as shown in FIG. 5 are formed. That is, the surface to be processed is modified, and a nano-level microstructure is formed on the surface to be processed.
- this microprotrusion is not clear in principle, it is presumed that it is formed by partial plasma discharge in liquid near the cathode electrode 5. Then, the surface modified method for producing a conductive material of the present invention, when it voltage applied is lower than the first voltages V 1 between the anode electrode 4 and cathode electrode 5, a partial liquid plasma discharge sufficiently occur without the microprojection (microstructure) is not formed, when it second voltage V 2 or more, will be a cathode electrode 5 to be processed material is oxidized by the generation of full plasma, roughness of the processed surface becomes several ⁇ m, and fine protrusions (fine structure) are not formed.
- the plasma discharge in liquid is performed when the temperature of the electrolytic solution in the vicinity of the cathode electrode 5 locally exceeds the boiling point due to application of a voltage, and a gas phase is generated in the vicinity of the cathode electrode 5. This is thought to be caused by the occurrence of plasma discharge. Therefore, it is preferable to apply the voltage between the anode electrode 4 and the cathode electrode 5 in the surface modification treatment step after the temperature of the electrolytic solution is in the range of 85 ° C to 100 ° C. This is because the temperature in the vicinity of the cathode electrode 5 can be efficiently raised to efficiently cause plasma discharge in liquid.
- the voltage application time in the surface modification treatment step can be set to an arbitrary time, for example, 5 seconds or more and 30 minutes or less. Incidentally, the shorter the voltage 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.
- an anode electrode and a cathode electrode immersed in an electrolytic solution can be used without using expensive equipment and advanced technology.
- a conductive material having a nano-level microstructure formed on the surface can be efficiently produced at low cost.
- a conductive material having a nano-level microstructure formed on the surface can exhibit various functions due to the microstructure.
- the method for producing the surface-modified conductive material of the present invention is not limited to the above example, and the method for producing the surface-modified conductive material of the present invention may be appropriately modified. it can.
- a commercially available cold-rolled steel sheet (C is 0.018 mass%, Si is 0.01 mass%, and Mn is 0.14 mass%: 3 mm width).
- the surface modification treatment having a length of 20 mm and a thickness of 0.7 mm was performed at various voltages.
- a platinum electrode was used as the anode electrode, the commercial cold-rolled steel sheet from which dirt was removed with dilute hydrochloric acid as the cathode electrode, and a concentration of 0.1 mol / L preheated to a temperature of 92 to 97 ° C. as an electrolytic solution.
- voltage of the surface modification treatment system using aqueous potassium carbonate solution - current characteristics were measured to obtain the first voltage V 1. Further, a voltage (second voltage V 2 ) at which the surface modification treatment system exhibits a complete plasma state was obtained.
- the length of the electrode immersed in the electrolytic solution was 20 mm, and the portion over the liquid surface of the electrolytic solution above it was covered with a heat resistant resin.
- the first current maximum value I MAX is 6.3 A
- I HALF (I MAX + I MIN ) / 2) was 3.5 A
- the first voltage V 1 was 80 V.
- the second voltage V 2 is also found to be a 140 V.
- a voltage having a magnitude shown in Table 1 was applied between the anode electrode and the cathode electrode for 30 minutes, and the surface of the material to be treated.
- a cold-rolled steel sheet having a surface modified was produced by a modification treatment.
- a plurality of surface-modified cold-rolled steel sheets were produced by changing the magnitude of the applied voltage in the range of 75V to 145V.
- a platinum electrode was used as an anode electrode
- the material to be treated was used as a cathode electrode
- an aqueous potassium carbonate solution having a concentration of 0.1 mol / L preheated to a temperature of 92 to 97 ° C. was used as an electrolytic solution.
- surface modification treatment system voltage - current characteristics were measured, respectively, were determined first voltage V 1. Further, the voltage (second voltage V 2 ) at which each surface modification treatment system exhibits a complete plasma state was determined.
- the length of the electrode immersed in the electrolytic solution was 20 mm, and the surface of the electrolytic solution was coated with a heat resistant resin.
- FIG. 3B shows the voltage-current characteristics when the material to be treated is SUS430
- FIG. 4A shows the voltage-current characteristics when the material to be treated is a nickel plate
- FIG. The voltage-current characteristic in case a processing material is a nickel wire is shown.
- FIG. 7 shows a SEM photograph of the surface of a nickel plate treated with an applied voltage of 100 V for 30 minutes.
- a surface modification treatment of SUS316L (a wire was rolled to a width of 1.5 mm, a length of 40 mm, and a thickness of 0.2 mm) as a material to be treated was performed.
- a mesh platinum electrode is used as the anode electrode
- the above SUS316L whose surface is mirror-polished with # 4000 sandpaper is used as the cathode electrode
- a concentration of 0. 1 mol / L of the voltage of the surface modification treatment system using aqueous potassium carbonate solution - measuring current characteristics were determined first voltage V 1.
- a voltage (second voltage V 2 ) at which the surface modification treatment system exhibits a complete plasma state was obtained.
- the length of the electrode immersed in the electrolytic solution was 20 mm.
- FIG. 5 (a) A TEM photograph of the microstructure of the surface-modified SUS316L in Production Example 7 is shown in FIG. 5 (a), and a TEM photograph of the microstructure of the surface-modified SUS316L in Production Example 8 is shown in FIG. 5 (b).
- FIG. 5 and 8 A photograph is shown in FIG. 5 and 8, it can be seen that many fine protrusions of about several tens of nanometers to several hundreds of nanometers are formed on the surface. As the fine protrusions, there are a large number of fine protrusions having a thin shape at the lower part than the vicinity of the tip, such as a mushroom.
- the size of the fine protrusions can be controlled by changing the applied voltage, and the size of the fine protrusions is 100 nm or less in Manufacturing Example 7 where the applied voltage is 90 V, and 200 mm in Manufacturing Example 8 where the applied voltage is 100 V. It is about ⁇ 300 nm. Also be inferred that the fine density (the density) of the protrusions can also be controlled by varying the applied voltage, the better the production example of the number density applied voltage of the fine protrusions 100 V 8 (about 32 / [mu] m 2), The applied voltage is lower than Production Example 7 (about 7 pieces / ⁇ m 2 ) with 90V.
- the composition range of SUS316L before surface modification is mass%, Ni: 12-15%, Cr: 16-18%, Mo: 2-3%. From FIG. 9, it can be seen that in the surface-modified SUS316L produced in Production Example 7, the Cr concentration of the fine protrusion is higher than that of the base portion, and the Ni concentration of the fine protrusion is lower than that of the base portion. . On the other hand, in the surface-modified SUS316L produced in Production Example 8, it can be seen that the Cr concentration of the fine protrusions is very low compared to the base part. Therefore, it can be seen from this result that the manufacturing method of the present invention may be able to manufacture a conductive material having fine protrusions with a controlled composition. Therefore, there is a possibility that the production method of the present invention can be used for producing a highly corrosion-resistant surface enriched with Cr, or for producing a catalyst surface lacking Cr and containing Ni as an effective element.
- a platinum electrode was used as the anode electrode
- SUS316 (length 20 mm, thickness 0.8 mm, width 2 mm) was used as the cathode electrode
- a 0.1 mol / L K 2 CO 3 solution was used as the electrolytic solution.
- a voltage changed between 90 V and 120 V was applied for 15 minutes to form fine protrusions having different sizes and distributions on the surface of the cathode electrode.
- An example of the SEM photograph of the surface of SUS316 is shown in FIG.
- the first voltage V 1 of the surface modification treatment system using SUS316 as the cathode voltage was 78V
- the second voltage V 2 was 125V.
- the water repellency and light emission characteristics of the surface of the surface-modified SUS316 were evaluated as follows.
- the surface-modified SUS316 was used, the relationship between the average number of fine protrusions per 1 ⁇ m (average density of fine protrusions: pieces / ⁇ m) and the ratio of the height to the contact width of water droplets was examined. 11 as shown. From this, the average existence density of the fine protrusions is high (that is, the number of fine protrusions is large, unless the average existence density of the fine protrusions is extremely low (that is, the number of fine protrusions is extremely small and the size of the fine protrusions is extremely large).
- FIG. 12 shows the emission characteristics of the surface of SUS316 having an average density of fine protrusions of 4.3 / ⁇ m, 1.9 / ⁇ m, and 0.3 / ⁇ m, and the emission of the SUS316 surface before surface modification.
- the numerical values in parentheses in the figure indicate the average diameter of the formed fine protrusions. From FIG.
- the surface-modified SUS316 has a clear emission intensity peak that is not found in the SUS316 before surface modification (with polishing) in the visible light region near the wavelength of 400 nm to 470 nm. From this, it is surmised that the surface of the surface-modified SUS316 can be used for a light emitting element or the like. Further, in the surface-modified SUS316, the relationship between the average number of fine protrusions per 1 ⁇ m (average density of fine protrusions: pieces / ⁇ m) and the net emission intensity (arbitrary unit) of the emission peak near the wavelength of 440 nm As a result, it was as shown in FIG.
- the net emission intensity is the height from the background to the peak top, with the straight line connecting between the wavelength of 390 nm and the wavelength of 490 nm as the background.
- the average density of fine protrusions was determined in the same manner as in the water repellency evaluation. From FIG. 13, it can be seen that the surface-modified SUS316 has higher emission characteristics than SUS316 (with a net emission intensity of almost 0) before the surface modification (with polishing). Further, it can be seen that the net emission intensity is stronger when the average density of fine protrusions is high (that is, the number of fine protrusions is large and the size of the fine protrusions is small). Accordingly, from the viewpoint of improving the light emission characteristics, it is preferable to form smaller fine protrusions at a low voltage.
- a conductive material having a nano-level microstructure formed on the surface can be efficiently manufactured at low cost.
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Abstract
Description
また、「不溶性陽極電極」とは、被処理表面を改質処理する際に、電解溶液中で実質的にイオン化しない導電性材料からなる電極を指す。
更に、「表面改質処理系」とは、不溶性陽極電極と、陰極電極(被処理材)と、電解溶液とを備え、被処理材の表面改質処理を行う系を指し、「表面改質処理系の電圧−電流特性」は、電解溶液中に浸漬した不溶性陽極電極と陰極電極との間に印加する電圧を連続的に変化させた際の電流値の変化を測定することで得ることができる。
なお、本発明の表面改質処理系の電圧−電流特性では、印加する電圧(正電圧)を高めていくと、電流値は、増加して極大値を取った後に減少し、その後、再び増加に転じるか、或いは、一定となる。そして、本発明では、印加する電圧を高めていった際の前記極大値(正電圧領域に最初に現れる極大値)を「第1電流極大値」とする。また、電流値が減少した後、増加に転じる前の極小値(正電圧領域に最初に現れる極小値)或いは一定となった値を「第1電流極小値」とする。
更に、「完全プラズマ状態」とは、放電時に、オレンジ色が混じった発光、或いは、オレンジ色が主体の発光が陰極電極表面を覆う状態を指す。そして、「完全プラズマ状態を呈する電圧」は、炭素鋼や合金鋼を含む鉄鋼材料や、ステンレス鋼およびZnやAlなどの大気加熱で高温酸化される材料では、電圧を30分間印加した際に陰極電極の表層が少なくとも100nmの厚さで酸化される電圧として規定できる。なお、陰極電極の表層が酸化された厚さは、陰極電極の断面をSEMで観察し、酸化層の平均厚さを測定することにより判断することができる。ここで、酸化層は、SEMの反射電子像により下地と明瞭に区別することができ、酸化層の平均厚さは、陰極電極の表面に平行な10μmの長さの断面について、酸化層の厚さの平均値をとることで評価できる。因みに、陰極電極の表層に空隙等が存在する場合、酸化された厚さには該空隙なども含まれる。
(1)まず、表面改質処理系に印加する電圧を変化させた際の電流の変化を測定し、電圧−電流特性を得る。この表面改質処理系の電圧−電流特性は、印加する電圧Vを高めていくと、電流Iの大きさは、増加して極大値を取った後に減少し、その後、再び増加に転じるか、増加せずに一定の値となる。
(2)次に、電圧−電流特性から、次第に増加した電流Iが最初に取る極大値である第1電流極大値IMAXを求める。また、第1電流極大値IMAXをとった後に次第に減少した電流Iが再び増加に転じる前の極小値(正電圧領域に最初に現れる極小値)或いは電流Iが増加せずに一定となった値である第1電流極小値IMINを求める。
(3)最後に、第1電流極大値IMAXと第1電流極小値IMINとの和の1/2の電流値IHALF(=(IMAX+IMIN)/2)を算出し、電圧−電流特性において電流値IHALFを示す第1電圧V1を求める。
その結果、図2に示すような電圧−電流特性が得られ、被処理物として市販冷延鋼板を用いたこの表面改質処理系では、第1電流極大値IMAXが6.3Aであり、第1電流極小値IMINが0.7Aであり、IHALF(=(IMAX+IMIN)/2)が3.5Aであり、第1電圧V1が80Vであることが分かった。また、第2電圧V2が140Vであることも分かった。
そして、各被処理材について、第1電圧以上、第2電圧未満の電圧を印加して表面改質処理を行ったところ、被処理表面にナノメートルサイズの微細突起が形成された。一例として、ニッケル板を100Vの印加電圧で30分間処理した際の表面のSEM写真を図7に示す。
その結果、図3(a)に示すような電圧−電流特性が得られ、被処理物としてSUS316Lを用いたこの表面改質処理系では、第1電流極大値IMAXが3.4Aであり、第1電流極小値IMINが0.6Aであり、IHALF(=(IMAX+IMIN)/2)が2.0Aであり、第1電圧V1が55Vであることが分かった。また、第2電圧V2が125Vであることも分かった。
製造例7および8で作製した表面改質されたSUS316Lの表面の微細構造をSEMおよびTEMで観察した。製造例7の表面改質されたSUS316Lの微細構造のTEM写真を図5(a)に示し、製造例8の表面改質されたSUS316Lの微細構造のTEM写真を図5(b)に、SEM写真を図8に示す。
図5および8より、表面に数十ナノメートル~数百ナノメートル程度の微細突起が多数形成されていることがわかる。なお、微細突起としては、マッシュルームのように先端付近よりも下部で細い形状を有しているものが多数存在している。ここで、微細突起のサイズは、印加電圧を変化させることで制御することができ、微細突起のサイズは、印加電圧90Vの製造例7では100nm以下であり、印加電圧100Vの製造例8では200~300nm程度である。また、微細突起の密度(存在密度)も印加電圧を変化させることで制御できると推察され、微細突起の数密度は印加電圧が100Vの製造例8(約32個/μm2)の方が、印加電圧が90Vの製造例7(約7個/μm2)より低い。
図9より、製造例7で作製した表面改質されたSUS316Lでは、微細突起部のCr濃度が下地部分と比較して高く、微細突起部のNi濃度が下地部分と比較して低いことが分かる。一方、製造例8で作製した表面改質されたSUS316Lでは、微細突起部のCr濃度が下地部分と比較して非常に低いことが分かる。よって、この結果より、本発明の製造方法では、組成を制御した微細突起を有する導電性材料を製造し得る可能性があることが分かる。従って、本発明の製造方法は、Crが濃化した高耐食表面の製造に使用したり、Crが欠乏した、Niを有効元素とする触媒表面の製造に使用したりできる可能性がある。
そして、表面改質されたSUS316の表面の撥水性および発光特性を以下のようにして評価した。
表面改質されたSUS316について、水滴を表面に垂らし、表面への水滴の接触幅(直径)に対する水滴の高さを測定したところ、高さ/接触幅は最大で0.62であった。表面改質前のSUS316の表面では、高さ/接触幅が0.38であったので、表面改質されたSUS316では、撥水性が向上していることが確かめられた。従って、表面改質されたSUS316は、水滴がついても落ちやすい、高耐食表面になっていると推察される。
また、表面改質されたSUS316で、1μmあたりの微細突起の平均数(微細突起の平均存在密度:個/μm)と、水滴の接触幅に対する高さの比との関係を調べたところ、図11に示すようになった。これより、微細突起の平均存在密度が著しく低い(即ち、微細突起数が著しく少なく、微細突起サイズが著しく大きい)場合を除き、微細突起の平均存在密度が高い(即ち、微細突起数が多く、微細突起サイズが小さい)ものよりも、微細突起の平均存在密度が低い(即ち、微細突起数が少なく、微細突起が大きい)もののほうが、撥水性が高い傾向があることが分かった。従って、撥水性を高める観点からは、ある程度高い電圧、例えば100V以上で微細突起を形成することが好ましいことがわかった。
なお、微細突起の平均存在密度は、SEMで得られた表面写真上に3μmの直線を引き、その直線が横切る微細突起数を、任意の10箇所について求めて、長さ1μmあたりに平均化したものである。
表面改質されたSUS316の表面の発光特性をフォトルミネッセンス測定により評価した。得られた表面のフォトルミネッセンススペクトルを図12に示す。なお、図12には、微細突起の平均存在密度が4.3個/μm、1.9個/μm、0.3個/μmのSUS316表面の発光特性および表面改質前のSUS316表面の発光特性を示しており、図中のカッコ内の数値は形成された微細突起の平均直径を示している。
図12より、表面改質されたSUS316では、波長400nm~470nm付近の可視光領域に、表面改質前(研磨あり)のSUS316にはない明確な発光強度ピークが得られることが分かる。このことから、表面改質されたSUS316の表面は発光素子などに利用することができると推察される。
また、表面改質されたSUS316で、1μmあたりの微細突起の平均数(微細突起の平均存在密度:個/μm)と、波長440nm付近の発光ピークの正味の発光強度(任意単位)との関係を調べたところ、図13に示すようになった。なお、正味の発光強度とは、波長390nmと波長490nmとの間を結ぶ直線をバックグランドとし、そのバックグランドからピークトップまでの高さである。因みに、微細突起の平均存在密度は、撥水性評価と同様にして求めた。
図13より、表面改質されたSUS316は、表面改質前(研磨あり)のSUS316(正味の発光強度は殆ど0)と比較して高い発光特性を有することが分かる。また、正味の発光強度は、微細突起の平均存在密度が高い(即ち、微細突起数が多く、微細突起サイズが小さい)もののほうが強くなっていることがわかる。従って、発光特性を向上させる観点からは、低電圧でより小さい微細突起を形成することが好ましい。
2 改質処理セル
3 電解溶液
4 陽極電極
5 陰極電極
6 直流電源
Claims (6)
- 電解溶液中に、不溶性陽極電極と、被処理表面を有する導電性材料からなる、陰極電極としての被処理材とを浸漬した後、前記電解溶液中に浸漬した前記不溶性陽極電極と、前記陰極電極としての被処理材との間に、第1電圧以上、第2電圧未満の電圧を印加し、前記被処理表面を改質処理する表面改質処理工程を含み、
前記第1電圧が、表面改質処理系の電圧−電流特性において、正電圧領域に最初に現れる第1電流極大値と、正電圧領域に最初に現れる第1電流極小値との和の1/2の電流値に対応する電圧であり、
前記第2電圧が、完全プラズマ状態を呈する電圧であることを特徴とする、表面改質された導電性材料の製造方法。 - 前記不溶性陽極電極と前記陰極電極との間に60V以上、140V未満の電圧を印加することを特徴とする、請求項1に記載の表面改質された導電性材料の製造方法。
- 前記導電性材料が、金属または合金材料であることを特徴とする、請求項1または2に記載の表面改質された導電性材料の製造方法。
- 前記導電性材料が、炭素鋼材であることを特徴とする、請求項2に記載の表面改質された導電性材料の製造方法。
- 前記導電性材料が、ステンレス鋼材であることを特徴とする、請求項2に記載の表面改質された導電性材料の製造方法。
- 前記電解溶液が、炭酸カリウム、炭酸ナトリウム、炭酸水素ナトリウムおよび炭酸アンモニウム、水酸化リチウム、水酸化ナトリウム、水酸化マグネシウム、水酸化カリウムおよび水酸化アンモニウム、塩化ナトリウム、塩化カリウム、塩化マグネシウムおよび塩化アンモニウム、リチウム、ナトリウム、マグネシウム、カリウムおよびアンモニウムの硫酸塩、リチウム、ナトリウム、マグネシウム、カリウムおよびアンモニウムの硝酸塩、リチウム、ナトリウム、マグネシウム、カリウムおよびアンモニウムのクエン酸塩、並びに、硫酸、硝酸、塩酸およびクエン酸よりなる群から選択される少なくとも1種を含む水溶液であることを特徴とする、請求項1~5の何れか1項に記載の表面改質された導電性材料の製造方法。
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