WO2014208610A1 - Conductive member - Google Patents

Conductive member Download PDF

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Publication number
WO2014208610A1
WO2014208610A1 PCT/JP2014/066869 JP2014066869W WO2014208610A1 WO 2014208610 A1 WO2014208610 A1 WO 2014208610A1 JP 2014066869 W JP2014066869 W JP 2014066869W WO 2014208610 A1 WO2014208610 A1 WO 2014208610A1
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WO
WIPO (PCT)
Prior art keywords
plating film
conductive member
plating
mass
noble metal
Prior art date
Application number
PCT/JP2014/066869
Other languages
French (fr)
Japanese (ja)
Inventor
洋介 西川
篤史 太田
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日本軽金属株式会社
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Publication of WO2014208610A1 publication Critical patent/WO2014208610A1/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/04—Alloys based on a platinum group metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1651—Two or more layers only obtained by electroless plating
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1837—Multistep pretreatment
    • C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • C23C28/025—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only with at least one zinc-based layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0206—Metals or alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a conductive member provided with a noble metal plating film on the surface of a metal substrate via a Ni plating film.
  • fuel cells have attracted attention as one of the environmentally friendly energy.
  • an electrolyte membrane is sandwiched between a pair of electrodes consisting of an anode and a cathode, and a plurality of fuel cell unit cells each having a separator on each of the anode side and the cathode side are stacked, and the stacking direction of this cell stack Current collectors are taken out by providing current collecting plates at both ends.
  • an Au plating film with a thickness of about 0.1 ⁇ m to 1 ⁇ m is generally provided.
  • the metal substrate is corroded and the contact resistance with the separator increases. There's a problem.
  • the contact resistance of the current collector plate may increase as the use of the fuel cell proceeds.
  • the present inventors have proposed a current collector plate in which an Au plating film is formed through a crystalline noble metal plating film (see Patent Document 4). That is, the present inventors have found out that the corrosion of the metal substrate and the increase in the contact resistance of the current collector plate are caused by the oxidation of the Ni plating film provided on the base, the noble metal plating film is made crystalline, the Ni plating The grain boundary of the noble metal plating film is blocked with Au by forming the Au plating film using a substitution reaction of Ni with the film. As a result, the oxidation of Ni can be suppressed to prevent the corrosion of the metal base material and the increase in contact resistance. Moreover, even if the Au plating film is made thinner than in the past, it is reliable over a long period of time. A current collector plate that can be used excellently has been realized.
  • JP 2003-217644 A (paragraph 0056) JP 2008-78104 A (paragraph 0090) JP 2008-146866 A (paragraph 0027) JP 2013-105629 A (Claim 2)
  • Au is chemically stable, has excellent corrosion resistance, has little change in contact resistance over time, and has excellent solderability, for example, the lead plate of the fuel cell described above, for example, lead In frames, bus bars, printed wiring boards, connection terminals, and the like, conductive members having an Au plating film are frequently used. However, it is ideal that the use can be reduced as much as possible due to the recent price increase.
  • the present inventors have conducted extensive studies on conductive members that can suppress contact resistance and have excellent corrosion resistance without using an Au plating film.
  • the present invention has been completed by finding that a conductive member capable of satisfying both the cost and quality can be obtained by solving these problems by combining with a high quality noble metal plating film.
  • an object of the present invention is to provide a conductive member that is excellent in cost performance, has low contact resistance, has excellent corrosion resistance, and can be used reliably over a long period of time.
  • the present invention is a conductive member provided with a noble metal plating film on the surface of a metal substrate through a Ni plating film, the Ni plating film contains 10% by mass or more of phosphorus (P),
  • the noble metal plating film contains one or more noble metals (more specifically, platinum group) selected from the group consisting of Pd, Pt, Rh, Ir, Os, and Ru, and is amorphous or microcrystalline.
  • the conductive member is characterized in that the film thickness is 20 nm or more and less than 200 nm.
  • the conductive member in the present invention includes a Ni plating film containing 10% by mass or more of phosphorus (P) in terms of P element.
  • P phosphorus
  • the reason why phosphorus is contained in an amount of 10% by mass or more is to obtain a Ni plating film having excellent corrosion resistance, and such a Ni plating film has an amorphous crystal structure.
  • By increasing the phosphorus content it is possible to show further excellent corrosion resistance, and preferably 11% by mass or more is included.
  • the phosphorus content of the Ni plating film tends to increase up to about 15% by increasing the concentration of the reducing agent in the plating solution.
  • the concentration of the reducing agent is further increased, it is difficult to increase the phosphorus content to 15% or more because only the Ni plating rate is reduced and no further phosphorus is taken into the Ni plating film. Therefore, the upper limit of the phosphorus content in the Ni plating film is substantially 15% by mass.
  • a plating bath obtained by adding phosphorous acid to a watt bath generally used as an electrolytic Ni plating bath is used, and a Ni plating film with a phosphorus content of about 10% by mass. Becomes amorphous. By adding citric acid or the like, the phosphorus content can be increased up to about 25% by mass.
  • the upper limit of the phosphorus content in the Ni plating film is 15% by mass even in the case of electrolytic plating treatment.
  • the thickness of the Ni plating film is preferably 1 ⁇ m or more and 10 ⁇ m or less, preferably 3 ⁇ m or more and 8 ⁇ m or less from the viewpoint of depositing the Ni plating film with a uniform thickness on the surface of the metal substrate. It is good to be. Even if the thickness of the Ni plating film is made thicker than 10 ⁇ m, the effect is saturated, and the cost may be increased.
  • the conductive member in the present invention is an amorphous or microcrystalline material containing any one or more precious metals selected from the group consisting of Pd, Pt, Rh, Ir, Os, and Ru on the Ni plating film.
  • the noble metal plating film is provided.
  • the noble metal plating film having an amorphous or microcrystalline crystal structure prevents the diffusion of Ni from the lower Ni plating film, thereby preventing an increase in contact resistance and a decrease in corrosion resistance. That is, if the noble metal plating film is crystalline, Ni may be diffused through the crystal grain boundary.
  • Ni when used in a high-temperature and high-humidity environment such as a current collector plate of a fuel cell, Ni is likely to be thermally diffused and oxidized or further hydrated to form insulating NiO or NiO (H 2 O) is formed and the contact resistance is lowered, and it is difficult to ensure corrosion resistance.
  • the amorphous or microcrystalline noble metal plating film means that the lattice points are not clearly observed by observation with an electron diffraction image of a transmission electron microscope (TEM).
  • the lattice points are clearly confirmed in the electron diffraction pattern, whereas when the plating film is microcrystalline, the lattice points are unclear, and when it is amorphous, Can be discriminated because the diffraction pattern becomes a halo pattern without confirming the lattice point.
  • it shall follow the Example mentioned later. The same applies to the Ni plating film described above.
  • the noble metal plating film may be made amorphous or microcrystalline so that it contains a eutectoid element, or the current density during the electrolytic plating process may be relatively low. By raising, an amorphous or microcrystalline noble metal plating film can be obtained. Especially, since it has a wide eutectoid composition range with many metals and is easy to form an amorphous plating, it is preferable that the noble metal plating film is phosphorus (P), boron (B), and tungsten (W).
  • P phosphorus
  • B boron
  • W tungsten
  • the noble metal plating film is good.
  • the content of the eutectoid element in the noble metal plating film if the content increases, the crystal structure of the noble metal plating film can be more reliably made amorphous or microcrystalline.
  • a noble metal plating film is formed, for example, by electroless plating treatment, if the content of the eutectoid element increases beyond 5%, the hardness of the noble metal plating film increases and heat treatment is performed. Therefore, it can be said that the upper limit of the eutectoid element content in the noble metal plating film is substantially about 5% by mass.
  • the thickness of the noble metal plating film is 20 nm or more and less than 200 nm, preferably 25 nm or more and less than 150 nm. That is, the contact resistance as a conductive member is suppressed by setting the film thickness of the noble metal plating film to less than 200 nm.
  • the film thickness of the noble metal plating film is thinner than 20 nm, the noble metal plating film cannot be deposited uniformly on the Ni plating film, and the diffusion of Ni cannot be prevented.
  • the means for forming the Ni plating film and the noble metal plating film may be an electroplating process or an electroless plating process, respectively. From the standpoint of superiority, it is preferable that both are formed by electroless plating. Further, the Ni plating film and the noble metal plating film may be provided on both the front and back surfaces of the metal base material according to the use of the conductive member, or may be provided only on one side surface.
  • examples of the metal base material include base materials such as copper alloys such as copper or brass, aluminum or aluminum alloys, iron alloys such as iron and stainless steel, etc. From the viewpoints of excellent workability, high electrical and thermal conductivity, and relatively low cost, an aluminum substrate made of aluminum or an aluminum alloy is preferable. In addition, when the above-mentioned Ni plating film and noble metal plating film are single-sided plating formed only on one side surface of the substrate, it is found from the standard oxidation-reduction potential E 0 (25 ° C.) of each metal shown below.
  • the aluminum or aluminum alloy used for the aluminum substrate is not particularly limited. And various aluminum alloys. Among these, a 5000 series aluminum alloy is preferable from the viewpoint of corrosion resistance, formability, strength, and cost.
  • the aluminum base is immersed in a zinc immersion bath to perform zinc replacement treatment, and the Ni plating film is formed on the aluminum base. It is good to form through a zinc layer.
  • a zinc immersion bath for example, an aqueous zinc oxide solution containing 4.1% by mass of zinc oxide and 25% by mass of sodium hydroxide can be diluted with ion-exchanged water to 400 ml / L and used.
  • the immersion temperature is about 15 to 30 ° C., and the immersion time is about 10 seconds to 3 minutes.
  • the immersion zinc bath is removed by immersing in a pickling bath,
  • the substituted zinc layer may be formed by dipping in a zinc immersion bath again.
  • the pickling bath at that time for example, an acid aqueous solution having an acid of nitric acid, sulfuric acid, hydrochloric acid or the like and having a concentration of 10 to 65 mass% can be used, the immersion temperature is about 15 to 30 ° C., and the immersion time is 10 Seconds to about 1 minute.
  • a predetermined pretreatment process such as degreasing or desmut treatment prior to the zinc replacement treatment to pretreat the aluminum substrate by a known method, or forming a connection terminal or the like on the aluminum substrate by pressing. May be performed.
  • the conductive member according to the present invention can be obtained by washing with water and drying.
  • the conductive member of the present invention is excellent in corrosion resistance and can suppress an increase in contact resistance even when used for a long time. Therefore, it can be used as various conductive members such as fuel cells, lead frames, bus bars, printed wiring boards, connection terminals, and the like. In particular, since Ni can be prevented from diffusing even in a high-temperature and high-humidity environment, it is suitable as a conductive member for forming a fuel cell, and particularly suitable for forming a current collector plate.
  • a conductive member having a low contact resistance and excellent conductivity and excellent corrosion resistance and long-term durability can be obtained without particularly providing an Au plating film. Therefore, the conductive member of the present invention satisfies both cost and quality at the same time, and can be used reliably over a long period of time.
  • FIG. 1 is an electron beam diffraction image of a Pd plating film in the test conductive member obtained in Example 1.
  • FIG. 2 is a schematic cross-sectional view for explaining the conductive member of the present invention.
  • FIG. 3 is a TEM image showing the cross section of the Ni plating film and the Pd plating film of the conductive member for test obtained in Example 1 (magnification 9,900 times).
  • FIG. 4 is a TEM image showing the state of the cross section of the Pd plating film in the test conductive member obtained in Example 1 (magnification: 285,000 times).
  • FIG. 5 is a schematic diagram ((a) side view, (b) perspective view) illustrating how the contact resistance of the test conductive member is measured.
  • FIG. 1 is an electron beam diffraction image of a Pd plating film in the test conductive member obtained in Example 1.
  • FIG. 2 is a schematic cross-sectional view for explaining the conductive member of the present invention.
  • FIG. 3 is a TEM image showing the
  • FIG. 6 is an electron diffraction image of a Pd plating film in the test conductive member obtained in Example 3.
  • FIG. 7 is a TEM image showing a cross-sectional state of the Ni plating film and the Pd plating film of the test conductive member obtained in Example 3 (magnification 9,900 times).
  • FIG. 8 is a TEM image showing the cross-sectional state of the Pd plating film in the test conductive member obtained in Example 3 (magnification: 285,000 times).
  • FIG. 9 is an electron diffraction image of the Ru plating film in the test conductive member obtained in Example 4.
  • FIG. 10 is a TEM image showing a cross-sectional state of the Ni plating film and the Ru plating film of the test conductive member obtained in Example 4 (magnification 9,900 times).
  • FIG. 11 is a TEM image showing the state of the cross section of the Ru plating film on the test conductive member obtained in Example 4 (magnification: 285,000 times).
  • 12 is an electron diffraction image of a Pd plating film in the test conductive member obtained in Comparative Example 2.
  • FIG. 13 is a TEM image showing the cross section of the Ni plating film and the Pd plating film of the conductive member for test obtained in Comparative Example 2 (magnification 9,900 times).
  • FIG. 14 is a TEM image showing a cross-sectional state of the Pd plating film in the test conductive member obtained in Comparative Example 2 (magnification: 285,000 times).
  • Example 1 [Preparation of conductive member for test] A 30 mm x 60 mm x 3 mm thick aluminum base material was cut out from a 3 mm thick aluminum alloy A5052-H34 material, and a weak alkaline degreasing agent (trade name: Top Alclean 161, manufactured by Okuno Pharmaceutical Co., Ltd.) at a concentration of 30 g / L. The sample was dipped in an aqueous solution diluted to 5 and degreased and washed at 55 ° C. for 5 minutes.
  • a weak alkaline degreasing agent trade name: Top Alclean 161, manufactured by Okuno Pharmaceutical Co., Ltd.
  • an etching agent containing 35% by mass of sodium hydroxide (Okuno Pharmaceutical Co., Ltd., trade name: Top Alsoft 108) is immersed in an aqueous solution diluted to a concentration of 50 g / L, and etched at 55 ° C. for 30 seconds. It was.
  • a desmut solution containing nitric acid (trade name: Top Desmatt N-20, manufactured by Okuno Pharmaceutical Co., Ltd.) is immersed in an aqueous solution diluted to a concentration of 100 ml / L, and desmutted at 25 ° C. for 1 minute. went.
  • a zinc treatment solution containing 20% by mass of sodium hydroxide and 3.6% by mass of zinc oxide (trade name: Substar, manufactured by Okuno Pharmaceutical Co., Ltd.)
  • the aluminum substrate was immersed for 30 seconds at 22 ° C. using a zinc immersion bath in which Zn-111) was diluted to a concentration of 500 ml / L.
  • an aqueous solution of nitric acid having a concentration of 62% by mass was used as a pickling bath, and the aluminum substrate was immersed for 30 seconds at 25 ° C., and the substituted zinc layer once formed on the surface of the aluminum substrate was peeled off.
  • the aluminum substrate was immersed at 22 ° C. for 30 seconds to form a substituted zinc layer of about 1 ⁇ m, and a zinc replacement treatment was performed.
  • a drug containing 19% by mass of sodium hypophosphite and 3.9% by mass of acetic acid (trade name: Top Nicolon RCH-MLF manufactured by Okuno Pharmaceutical Co., Ltd.) and 36% by mass of nickel sulfate are contained.
  • the Ni plating solution (trade name: Top Nicolon RCH-1LF, manufactured by the same company) was diluted at 90 ° C. with a Ni plating bath that was diluted with water to a concentration of 130 ml / L and 40 ml / L, respectively. An electroless Ni plating treatment for immersion for 35 minutes was performed.
  • this Ni plating film contained 11 mass% of phosphorus (P) in terms of P element, and the crystal structure was amorphous.
  • a drug containing 13% by mass of a complexing agent (trade name: Top Paras PDP-M manufactured by Okuno Pharmaceutical Co., Ltd.), 7.2% by mass of a palladium salt, and 5.6% by mass of a complexing agent were contained.
  • Drug product name: Topparas PDP-A
  • drug containing 41% by mass of phosphate Product name: Topparas PDP-B
  • sodium hydroxide 7% by mass complexing agent Containing 0.29% by mass
  • complexing agent Containing 0.29% by mass (trade name: Top Palas PDP-C), 44% by mass of phosphate (trade name: Top Paras PDP-D), and 17 ethylenediamine.
  • a drug containing 16% by mass, 16% by mass of a complexing agent, and 0.1% by mass of a sulfur-containing compound (trade name: Top Paras PDP-E manufactured by the same company), respectively, at concentrations of 200 ml / L, 12 ml / L, and 70 ml / L, 30ml / L, 3.5ml / L, 100ml / L
  • a Pd plating film (noble metal plating film) having a film thickness of 49 nm was formed on the Ni plating film.
  • this Pd plating film contained 2 mass% of phosphorus (P) in terms of P element, and the crystal structure was amorphous.
  • FIG. 1 shows an electron beam diffraction image (halo pattern) of TEM obtained with this Pd plating film.
  • test conductive member 1 according to Example 1 provided with a Pd plating film 5 was obtained.
  • all the amount of process liquids, such as a plating bath used at said each process were performed as 2L.
  • FIG. 3 shows the result of cross-sectional observation with a transmission electron microscope (TEM) of the test conductive member 1 obtained in Example 1 (9,900 times magnification).
  • TEM transmission electron microscope
  • FIG. 4 is a TEM image obtained by observing the cross section of the Pd plating film at 285,000 times. In this TEM image, a clear crystal lattice is not confirmed, and it can be seen that the Pd plating film is amorphous.
  • each film thickness measurement of the Ni plating film and the noble metal plating film in the test conductive member 1 obtained above was performed using a fluorescent X-ray film thickness meter (Fischer Scope XDV ⁇ manufactured by Fischer Instruments). I went.
  • the phosphorus (P) content in the Ni plating film is measured by preparing the same Ni plating bath as used above and precipitating it on a Cu plate (Cu, which is a heavy element, is more fluorescent X-ray than Al). It was measured with a fluorescent X-ray apparatus (RIX2100, manufactured by Rigaku Corporation), and the P content was quantitatively analyzed by the FP method (fundamental parameter method).
  • Ni plating containing Ni Ni-B plating
  • Pd plating was deposited on a Cu plate, and then the same Pd plating bath as used above
  • the Pd plating was deposited using, and the P content was quantitatively analyzed by the FP method using a fluorescent X-ray apparatus in the same manner as in the case of the Ni plating film.
  • Cl element content rate derived from ruthenium chloride was quantitatively analyzed by FP method by EPMA.
  • the noble metal plating film used for TEM observation had a film thickness of about 100 nm, the electron diffraction region was limited using an aperture having a diameter of 200 nm, and an electron diffraction image (limited field electron diffraction image) of only the target location.
  • the observation conditions were adjusted so that For each plating film, when the lattice point is clearly confirmed in the obtained electron beam diffraction image, there is no crystallinity, and when the lattice point is unknown, there is no microcrystalline and lattice point, and the halo pattern is When confirmed, it was determined to be amorphous.
  • the contact resistance was measured as follows. As shown in FIG. 5 (a), the noble metal plating film side is brought into contact with the comparison plate 7, and these are sandwiched between the upper plate 6 and the lower plate 8, and the test conductive member 1 is applied while applying a surface pressure from above and below. The contact resistance value of was measured. In general, the contact resistance required for the current collector plate of the fuel cell is about 10 m ⁇ ⁇ cm 2 when the surface pressure is 1 MPa assuming a normal use mode. It was found that the contact resistance when the surface pressure was 1 MPa was about 0.05 m ⁇ ⁇ cm 2 , indicating a very good contact resistance.
  • the upper plate 6, the comparison plate 7, and the lower plate 8 each have a thickness of 0.1 ⁇ m via a Ni plating film having a thickness of 5 ⁇ m on both front and back surfaces of an aluminum plate (A5052 material) of 30 mm ⁇ 60 mm ⁇ thickness 3 mm.
  • a contact resistance measurement sample in which the vertical and horizontal directions are alternately stacked is prepared, and the contact between the test conductive member 1 and the comparison plate 7 is prepared.
  • the contact resistance (m ⁇ ⁇ cm 2 ) is measured by measuring the voltage V between the test conductive member 1 and the comparison plate 7 by passing a current I of 2 A between the upper plate 6 and the lower plate 8.
  • V ⁇ S / I V ⁇ 9/2.
  • Example 2 A test conductive member according to Example 2 was obtained in the same manner as in Example 1 except that the electroless Pd plating treatment was performed with the immersion time in the Pd plating bath being 14 minutes.
  • the obtained conductive member for test was provided with a Ni plating film having a phosphorus content of 11% by mass and a film thickness of 5.2 ⁇ m, and a Pd plating film having a phosphorus content of 2% by mass and a film thickness of 87 nm. All the plating films were amorphous in crystal structure.
  • the contact resistance of the test conductive member according to Example 2 was measured in the same manner as in Example 1, the contact resistance when the surface pressure was 1 MPa was about the same as that in Example 1.
  • Other evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 3 A test conductive member according to Example 3 was obtained in the same manner as in Example 1 except that the electroless Pd plating treatment was performed as follows. That is, Example 3 contains 2.5% by mass of ethylenediamine and 4.0% by mass of a palladium salt (trade name: Muden Noble PD-1) and 11% by mass of hypophosphite. Drug (trade name: Muden Noble PD-2 made by the company), 2.1 mass% ethylenediamine, 6.0 mass% hypophosphite, and 5.4 mass% complexing agent (made by the company) Product name: Muden Noble PD-3) is immersed in water at 55 ° C.
  • a palladium salt trade name: Muden Noble PD-1
  • Drug trade name: Muden Noble PD-2 made by the company
  • Product name: Muden Noble PD-3 is immersed in water at 55 ° C.
  • the phosphorus content was 11% by mass and the Ni plating film having a film thickness of 5.3 ⁇ m was provided, and the phosphorus content was 5% by mass and the film thickness was 53 nm.
  • the Pd plating film was provided, and any of the plating films had an amorphous crystal structure.
  • FIG. 6 shows an electron beam diffraction image (halo pattern) of TEM obtained with the Pd plating film.
  • the obtained conductive member for test was subjected to cross-sectional observation with a transmission electron microscope (TEM) (magnification 9,900 times).
  • TEM transmission electron microscope
  • FIB focused ion beam
  • FIG. 8 is a TEM image obtained by observing the cross section of the Pd plating film at 285,000 times. In this TEM image, a clear crystal lattice is not confirmed, and it can be seen that the Pd plating film is amorphous.
  • Example 4 A test conductive member according to Example 4 was obtained in the same manner as in Example 1 except that a noble metal plating film composed of a ruthenium (Ru) plating film was formed as follows. That is, after the Ni plating film was formed and washed in the same manner as in Example 1, the degreasing agent (trade name: Okure Pharmaceutical Co., Ltd., trade name: A-screen 801) was diluted with water so as to be 50 g / L. Degreasing was performed by immersing in a degreasing bath at 50 ° C. for 5 minutes.
  • a noble metal plating film composed of a ruthenium (Ru) plating film was formed as follows. That is, after the Ni plating film was formed and washed in the same manner as in Example 1, the degreasing agent (trade name: Okure Pharmaceutical Co., Ltd., trade name: A-screen 801) was diluted with water so as to be 50 g / L. Degreasing was performed by immersing in
  • Example 4 while containing a Ni plating film having a phosphorus content of 11% by mass and a film thickness of 5.6 ⁇ m, the Cl content is 2.5% by mass and the Ru plating having a film thickness of 93 nm.
  • a test conductive member provided with a film was obtained.
  • the crystal structure of the Ni plating film was amorphous, and the crystal structure of one Ru plating film was microcrystalline.
  • FIG. 9 shows an electron beam diffraction image (having an unknown lattice point) of TEM obtained with this Ru plating film.
  • Example 4 For the test conductive member according to Example 4, when the contact resistance was measured in the same manner as in Example 1, the contact resistance when the surface pressure was 1 MPa was about the same as in Example 1. Other evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
  • the obtained conductive member for test was subjected to cross-sectional observation with a transmission electron microscope (TEM) (magnification 9,900 times).
  • TEM transmission electron microscope
  • the cross section of the Ni plating film and the Ru plating film was observed using a FIB (focused ion beam) method.
  • FIG. 11 is a TEM image obtained by observing the cross section of the Ru plating film at 285,000 times. According to this, it can be confirmed that the Ru plating film formed by the electrolytic plating treatment is composed of microcrystals having a crystal lattice domain of about 5 to 10 nm.
  • Example 1 In the same manner as in Example 1 except that the electroless Ni plating treatment was performed as follows, and the bath temperature of the Pd plating bath was 57 ° C. and the immersion time was 8 minutes, the electroless Pd plating treatment was performed. A test conductive member according to Example 1 was obtained. That is, in this Comparative Example 1, a drug containing 11% by mass of sodium hypophosphite and 24% by mass of a complexing agent (trade name: ICP Nicolon GSR-M manufactured by Okuno Pharmaceutical Co., Ltd.) and 36% by mass of nickel sulfate were added.
  • the Ni plating solution contained (trade name: ICP Nicolon GSR-1 manufactured by the company) was diluted at 80 ° C. with a Ni plating bath that was diluted with water to a concentration of 150 ml / L and 50 ml / L, respectively. An electroless Ni plating treatment for immersion for 30 minutes was performed.
  • the phosphorus content was 6% by mass and the Ni plating film having a film thickness of 5.1 ⁇ m was provided, and the phosphorus content was 2% by mass and the film thickness was 52 nm.
  • the Pd plating film was provided.
  • the crystal structure of the Ni plating film was crystalline, and the crystal structure of the Pd plating film was amorphous.
  • the test conductive member according to Comparative Example 1 was evaluated in the same manner as in Example 1. As a result, although the contact resistance showed a good value, as shown in Table 1, none of the evaluations regarding corrosion resistance and durability were satisfactory.
  • Comparative Example 2 A test conductive member according to Comparative Example 2 was obtained in the same manner as in Example 1 except that the electroless Pd plating treatment was performed as follows. That is, in Comparative Example 2, a drug containing a chelating agent (trade name: Paratop LP-M manufactured by Okuno Pharmaceutical Co., Ltd.) and a drug containing 7% by mass of a palladium salt (trade name manufactured by the company: Paratop LP-) A), a drug containing 41% by mass of a reducing agent (trade name: Paratop LP-B) and a drug containing 4.4% by mass of a complexing agent (trade name: Paratop LP-C) ) Is immersed in water at 60 ° C.
  • a drug containing a chelating agent trade name: Paratop LP-M manufactured by Okuno Pharmaceutical Co., Ltd.
  • a drug containing 7% by mass of a palladium salt trade name manufactured by the company: Paratop LP-
  • the phosphorus content was 11% by mass and the Ni plating film having a film thickness of 5.6 ⁇ m was provided, and the phosphorus content was 1% by mass and the film thickness was 63 nm.
  • the Pd plating film was provided.
  • the crystal structure of the Ni plating film was amorphous, and the crystal structure of the Pd plating film was crystalline.
  • FIG. 12 shows an electron beam diffraction image (clear lattice points) of TEM obtained with the Pd plating film.
  • Various evaluations were performed on the test conductive member according to Comparative Example 2 in the same manner as in Example 1. As a result, although the contact resistance showed a good value, as shown in Table 1, none of the evaluations regarding corrosion resistance and durability were satisfactory.
  • FIG. 13 is a TEM image obtained by observing a cross section of the Pd plating film at 285,000 times, and a domain of a stripe pattern of a crystal lattice exceeding several tens of nm can be confirmed.
  • 1 conductive member
  • 2 aluminum substrate
  • 3 substituted zinc layer
  • 4 Ni plating film
  • 5 Pd plating film
  • 6 upper plate
  • 7 comparison plate
  • 8 lower plate.

Abstract

　The present invention provides a conductive member having exceptional cost performance, low contact resistance, and exceptional corrosion resistance, the conductive member being capable of being used highly reliably for a long period of time. A conductive member provided with a Ni-plated film and a noble-metal-plated film on the surface of a metallic substrate, the conductive member being characterized in that the Ni-plated film contains 10 mass% or more phosphorus (P), and the noble-metal-plated film includes one or more noble metals selected from the group comprising Pd, Pt, Rh, Ir, Os, and Ru, is amorphous or microcrystalline, and has a thickness of 20 nm and over to less than 200 nm.

Description

導電部材Conductive member
　この発明は、金属製基材の表面にＮｉめっき皮膜を介して貴金属めっき皮膜を備えた導電部材に関する。 The present invention relates to a conductive member provided with a noble metal plating film on the surface of a metal substrate via a Ni plating film.
　近年、環境を配慮したエネルギーのひとつとして燃料電池が注目されている。一般に、燃料電池は、アノード及びカソードからなる一対の電極間に電解質膜を挟み込み、アノード側とカソード側にそれぞれセパレータを配した燃料電池単位セルを複数個積層させて、このセル積層体の積層方向の両末端に集電板を設けて電流を取り出すようにしている。 In recent years, fuel cells have attracted attention as one of the environmentally friendly energy. In general, in a fuel cell, an electrolyte membrane is sandwiched between a pair of electrodes consisting of an anode and a cathode, and a plurality of fuel cell unit cells each having a separator on each of the anode side and the cathode side are stacked, and the stacking direction of this cell stack Current collectors are taken out by providing current collecting plates at both ends.
　このうち、例えば、集電板には、効率的に電流を回収するために接触抵抗が小さいことが求められ、これまでに、金属製基材の表面に金（Au）めっきを施したものが使われている（例えば特許文献１～３参照）。ところが、燃料電池を広く実用化するにあたっては、コストを如何に下げるかがひとつの大きな課題であり、高価なＡｕめっき皮膜の使用をできるだけ抑えたいという要望がある。特に昨今の金の価格高騰によってその傾向はますます顕著である。 Among these, for example, current collector plates are required to have low contact resistance in order to efficiently collect current, and so far, the surface of a metal base material has been subjected to gold (Au) plating. (See, for example, Patent Documents 1 to 3). However, when the fuel cell is widely put into practical use, how to reduce the cost is one big problem, and there is a demand to suppress the use of the expensive Au plating film as much as possible. In particular, this trend is more pronounced with the recent rise in gold prices.
　しかしながら、従来、０．１μｍ～１μｍ程度のＡｕめっき皮膜を設けるのが一般的であるところ、これを薄くしていくと金属製基材が腐食したり、セパレータとの接触抵抗が増大してしまう問題がある。また、Ａｕめっき皮膜の膜厚が確保されていても、燃料電池の使用が進むにつれて集電板の接触抵抗が増加してしまうことがある。 However, conventionally, an Au plating film with a thickness of about 0.1 μm to 1 μm is generally provided. However, if the thickness is reduced, the metal substrate is corroded and the contact resistance with the separator increases. There's a problem. Even if the thickness of the Au plating film is secured, the contact resistance of the current collector plate may increase as the use of the fuel cell proceeds.
　そこで、本発明者らは、結晶質の貴金属めっき皮膜を介してＡｕめっき皮膜を形成した集電板を提案している（特許文献４参照）。すなわち、本発明者らは、金属製基材の腐食や集電板の接触抵抗の増加が下地に設けるＮｉめっき皮膜の酸化に起因することを突き止め、貴金属めっき皮膜を結晶質にして、Ｎｉめっき皮膜のＮｉとの置換反応を利用してＡｕめっき皮膜を形成することで、貴金属めっき皮膜の粒界がＡｕで塞がれるようにしている。これによりＮｉの酸化が抑制されて、金属製基材の腐食や接触抵抗の増加を防止することができ、しかも、従来に比べてＡｕめっき皮膜を薄くしても、長期に亘って信頼性に優れて使用できる集電板を実現している。 Therefore, the present inventors have proposed a current collector plate in which an Au plating film is formed through a crystalline noble metal plating film (see Patent Document 4). That is, the present inventors have found out that the corrosion of the metal substrate and the increase in the contact resistance of the current collector plate are caused by the oxidation of the Ni plating film provided on the base, the noble metal plating film is made crystalline, the Ni plating The grain boundary of the noble metal plating film is blocked with Au by forming the Au plating film using a substitution reaction of Ni with the film. As a result, the oxidation of Ni can be suppressed to prevent the corrosion of the metal base material and the increase in contact resistance. Moreover, even if the Au plating film is made thinner than in the past, it is reliable over a long period of time. A current collector plate that can be used excellently has been realized.
特開２００３－２１７６４４号公報（段落0056）JP 2003-217644 A (paragraph 0056) 特開２００８－７８１０４号公報（段落0090）JP 2008-78104 A (paragraph 0090) 特開２００８－１４６８６６号公報（段落0027）JP 2008-146866 A (paragraph 0027) 特開２０１３－１０５６２９号公報（請求項2）JP 2013-105629 A (Claim 2)
　Ａｕは化学的に安定であり、耐食性に優れ、接触抵抗値の経時的変化が少なく、はんだ付け性にも優れるといった特徴を有することから、上述した燃料電池の集電板をはじめ、例えば、リードフレームやバスバー、プリント配線基板、接続端子等では、Ａｕめっき皮膜を備えた導電部材が多用されている。しかしながら、近年の価格高騰により、その使用をできるだけ少なくできるのが理想である。 Since Au is chemically stable, has excellent corrosion resistance, has little change in contact resistance over time, and has excellent solderability, for example, the lead plate of the fuel cell described above, for example, lead In frames, bus bars, printed wiring boards, connection terminals, and the like, conductive members having an Au plating film are frequently used. However, it is ideal that the use can be reduced as much as possible due to the recent price increase.
　そこで、本発明者らは、Ａｕめっき皮膜を使用せずとも、接触抵抗を抑えることができ、耐食性にも優れた導電部材について鋭意検討を重ねた結果、Ｎｉめっき皮膜と非晶質又は微結晶質の貴金属めっき皮膜との組み合わせにより、これらの課題を解決して、コスト性と品質を同時に満足できる導電部材が得られることを見出し、本発明を完成させた。 Therefore, the present inventors have conducted extensive studies on conductive members that can suppress contact resistance and have excellent corrosion resistance without using an Au plating film. The present invention has been completed by finding that a conductive member capable of satisfying both the cost and quality can be obtained by solving these problems by combining with a high quality noble metal plating film.
　したがって、本発明の目的は、コスト性に優れながら、接触抵抗が小さく、しかも、耐食性に優れて長期に亘って信頼性良く使用することができる導電部材を提供することにある。 Therefore, an object of the present invention is to provide a conductive member that is excellent in cost performance, has low contact resistance, has excellent corrosion resistance, and can be used reliably over a long period of time.
　すなわち、本発明は、金属製基材の表面にＮｉめっき皮膜を介して貴金属めっき皮膜を備えた導電部材であって、前記Ｎｉめっき皮膜はリン（Ｐ）を１０質量％以上含み、また、前記貴金属めっき皮膜は、Ｐｄ、Ｐｔ、Ｒｈ、Ｉｒ、Ｏｓ、及びＲｕからなる群から選ばれたいずれか１以上の貴金属（より詳しくは白金族）を含むと共に、非晶質又は微結晶質であり、かつ、膜厚が２０ｎｍ以上２００ｎｍ未満であることを特徴とする導電部材である。 That is, the present invention is a conductive member provided with a noble metal plating film on the surface of a metal substrate through a Ni plating film, the Ni plating film contains 10% by mass or more of phosphorus (P), The noble metal plating film contains one or more noble metals (more specifically, platinum group) selected from the group consisting of Pd, Pt, Rh, Ir, Os, and Ru, and is amorphous or microcrystalline. The conductive member is characterized in that the film thickness is 20 nm or more and less than 200 nm.
　本発明における導電部材は、Ｐ元素換算でリン（Ｐ）を１０質量％以上含んだＮｉめっき皮膜を備える。リンを１０質量％以上含有させるのは耐食性に優れたＮｉめっき皮膜を得るためであり、このようなＮｉめっき皮膜は非晶質の結晶組織を有する。リンの含有量を増やすことで更に優れた耐食性を示すことができ、好ましくは１１質量％以上含むのがよいが、例えば無電解Ｎｉめっき処理により形成する場合には、一般に、次亜リン酸や次亜リン酸ナトリウム等のような還元剤としてＮｉめっき液を構成する上で、めっき液中の還元剤の濃度を増やすことで、Ｎｉめっき皮膜のリン含有率は１５％程度までは増える傾向にあるが、それ以上に還元剤の濃度を増やしても、Ｎｉめっき速度が低下するだけで、それ以上Ｎｉめっき皮膜中にリンが取り込まれず、リン含有率を１５％以上に上げることは困難であることから、実質的にはＮｉめっき皮膜におけるリンの含有量の上限は１５質量％である。一方、電解めっき処理により形成する場合には、電解Ｎｉめっき浴として一般的に使用されるワット浴に亜リン酸を加えためっき浴等が使用され、リン含有率１０質量％程度でＮｉめっき皮膜は非晶質になる。クエン酸等の添加により、２５質量％程度までリン含有率を増大することも可能であるが、リン含有率が１５質量％を超えると、水素発生が過大となり、Ｎｉめっきの電流効率が極端に低下することから、電解めっき処理場合にもＮｉめっき皮膜におけるリンの含有量の上限は１５質量％である。 The conductive member in the present invention includes a Ni plating film containing 10% by mass or more of phosphorus (P) in terms of P element. The reason why phosphorus is contained in an amount of 10% by mass or more is to obtain a Ni plating film having excellent corrosion resistance, and such a Ni plating film has an amorphous crystal structure. By increasing the phosphorus content, it is possible to show further excellent corrosion resistance, and preferably 11% by mass or more is included. For example, when formed by electroless Ni plating, in general, hypophosphorous acid or In configuring the Ni plating solution as a reducing agent such as sodium hypophosphite, the phosphorus content of the Ni plating film tends to increase up to about 15% by increasing the concentration of the reducing agent in the plating solution. However, even if the concentration of the reducing agent is further increased, it is difficult to increase the phosphorus content to 15% or more because only the Ni plating rate is reduced and no further phosphorus is taken into the Ni plating film. Therefore, the upper limit of the phosphorus content in the Ni plating film is substantially 15% by mass. On the other hand, in the case of forming by electrolytic plating, a plating bath obtained by adding phosphorous acid to a watt bath generally used as an electrolytic Ni plating bath is used, and a Ni plating film with a phosphorus content of about 10% by mass. Becomes amorphous. By adding citric acid or the like, the phosphorus content can be increased up to about 25% by mass. However, if the phosphorus content exceeds 15% by mass, hydrogen generation becomes excessive and the current efficiency of Ni plating becomes extremely high. Since it decreases, the upper limit of the phosphorus content in the Ni plating film is 15% by mass even in the case of electrolytic plating treatment.
　このＮｉめっき皮膜の膜厚については、金属製基材の表面に均一な厚みでＮｉめっき皮膜が析出されるようにする観点から、１μｍ以上１０μｍ以下であるのがよく、好ましくは３μｍ以上８μｍ以下であるのがよい。Ｎｉめっき皮膜の膜厚を１０μｍより厚くしても効果が飽和し、かえってコストが増すおそれがある。 The thickness of the Ni plating film is preferably 1 μm or more and 10 μm or less, preferably 3 μm or more and 8 μm or less from the viewpoint of depositing the Ni plating film with a uniform thickness on the surface of the metal substrate. It is good to be. Even if the thickness of the Ni plating film is made thicker than 10 μm, the effect is saturated, and the cost may be increased.
　また、本発明における導電部材は、Ｎｉめっき皮膜の上に、Ｐｄ、Ｐｔ、Ｒｈ、Ｉｒ、Ｏｓ、及びＲｕからなる群から選ばれたいずれか１以上の貴金属を含む非晶質又は微結晶質の貴金属めっき皮膜を備える。この貴金属めっき皮膜が非晶質又は微結晶質の結晶組織を有することで、下層のＮｉめっき皮膜からのＮｉの拡散を防いで、接触抵抗の増加や耐食性が低下するのを防止する。すなわち、貴金属めっき皮膜が結晶質であると、その結晶粒界を通じてＮｉが拡散してしまうおそれがある。特に、燃料電池の集電板等のように、高温高湿度の環境下で使用されるとＮｉが熱拡散して酸化され易く、或いは更に水和されて、絶縁性のＮｉＯやＮｉＯ(Ｈ2Ｏ）を形成し、接触抵抗を低下させてしまうほか、耐食性を確保するのが難しくなってしまう。ここで、非晶質又は微結晶質の貴金属めっき皮膜とは、透過型電子顕微鏡（TEM）の電子線回折像による観察で格子点が明確に観察されないものを意味する。すなわち、めっき皮膜が結晶質の場合には電子線回折像において格子点が明りょうに確認されるのに対して、微結晶質の場合には格子点が不明りょうとなり、また、非晶質の場合には格子点は確認されずに回折パターンがハローパターンとなることから判別が可能である。なお、測定条件については、後述する実施例に従うものとする。また、先に述べたＮｉめっき皮膜についても同様である。 Further, the conductive member in the present invention is an amorphous or microcrystalline material containing any one or more precious metals selected from the group consisting of Pd, Pt, Rh, Ir, Os, and Ru on the Ni plating film. The noble metal plating film is provided. The noble metal plating film having an amorphous or microcrystalline crystal structure prevents the diffusion of Ni from the lower Ni plating film, thereby preventing an increase in contact resistance and a decrease in corrosion resistance. That is, if the noble metal plating film is crystalline, Ni may be diffused through the crystal grain boundary. In particular, when used in a high-temperature and high-humidity environment such as a current collector plate of a fuel cell, Ni is likely to be thermally diffused and oxidized or further hydrated to form insulating NiO or NiO (H 2 O) is formed and the contact resistance is lowered, and it is difficult to ensure corrosion resistance. Here, the amorphous or microcrystalline noble metal plating film means that the lattice points are not clearly observed by observation with an electron diffraction image of a transmission electron microscope (TEM). In other words, when the plating film is crystalline, the lattice points are clearly confirmed in the electron diffraction pattern, whereas when the plating film is microcrystalline, the lattice points are unclear, and when it is amorphous, Can be discriminated because the diffraction pattern becomes a halo pattern without confirming the lattice point. In addition, about a measurement condition, it shall follow the Example mentioned later. The same applies to the Ni plating film described above.
　貴金属めっき皮膜が非晶質又は微結晶質となるためには、例えば、貴金属めっき皮膜が共析元素を含むようにして非晶質又は微結晶質としたり、電解めっき処理の際の電流密度を比較的高めることによって非晶質又は微結晶質の貴金属めっき皮膜を得ることができる。なかでも、多くの金属と幅広い共析組成範囲を有し、非晶質めっきを形成しやすいことから、好ましくは、貴金属めっき皮膜が、リン（Ｐ）、ホウ素（Ｂ）、及びタングステン（Ｗ）からなる群から選ばれたいずれか１以上の共析元素を２質量％以上含むようにするのがよく、より好ましくは、リン（Ｐ）を２質量％以上含んだ非晶質又は微結晶質の貴金属めっき皮膜であるのがよい。 In order for the noble metal plating film to be amorphous or microcrystalline, for example, the noble metal plating film may be made amorphous or microcrystalline so that it contains a eutectoid element, or the current density during the electrolytic plating process may be relatively low. By raising, an amorphous or microcrystalline noble metal plating film can be obtained. Especially, since it has a wide eutectoid composition range with many metals and is easy to form an amorphous plating, it is preferable that the noble metal plating film is phosphorus (P), boron (B), and tungsten (W). It is preferable to contain 2% by mass or more of any one or more eutectoid elements selected from the group consisting of, more preferably, amorphous or microcrystalline material containing 2% by mass or more of phosphorus (P). The noble metal plating film is good.
　ここで、貴金属めっき皮膜における共析元素の含有量については、その含有量が増えれば、貴金属めっき皮膜の結晶組織をより確実に非晶質又は微結晶質にすることができることから、共析元素の含有量が高い場合が好ましいが、例えば無電解めっき処理により貴金属めっき皮膜を形成する場合、共析元素の含有率が５％を超えて増大すると、貴金属めっき皮膜の硬度が増し、熱処理を行うとクラックが入りやすくなるであることからして、貴金属めっき皮膜における共析元素の含有量の上限は実質的に５質量％程度であると言うことができる。 Here, regarding the content of the eutectoid element in the noble metal plating film, if the content increases, the crystal structure of the noble metal plating film can be more reliably made amorphous or microcrystalline. However, when a noble metal plating film is formed, for example, by electroless plating treatment, if the content of the eutectoid element increases beyond 5%, the hardness of the noble metal plating film increases and heat treatment is performed. Therefore, it can be said that the upper limit of the eutectoid element content in the noble metal plating film is substantially about 5% by mass.
　また、本発明において、貴金属めっき皮膜の膜厚は２０ｎｍ以上２００ｎｍ未満、好ましくは２５ｎｍ以上１５０ｎｍ未満である。すなわち、貴金属めっき皮膜の膜厚を２００ｎｍ未満にすることで、導電部材としての接触抵抗を抑えるようにする。一方、貴金属めっき皮膜の膜厚が２０ｎｍより薄くなると、Ｎｉめっき皮膜上に均一に貴金属めっき皮膜を析出させることができず、Ｎｉの拡散を防止することができない。 In the present invention, the thickness of the noble metal plating film is 20 nm or more and less than 200 nm, preferably 25 nm or more and less than 150 nm. That is, the contact resistance as a conductive member is suppressed by setting the film thickness of the noble metal plating film to less than 200 nm. On the other hand, when the film thickness of the noble metal plating film is thinner than 20 nm, the noble metal plating film cannot be deposited uniformly on the Ni plating film, and the diffusion of Ni cannot be prevented.
　本発明において、Ｎｉめっき皮膜及び貴金属めっき皮膜を形成する手段としては、それぞれ個別に電解めっき処理であってもよく、無電解めっき処理であってもよいが、コスト性や膜厚の均一性に優れる観点から、好ましくは、いずれも無電解めっき処理により形成されたものであるのがよい。また、Ｎｉめっき皮膜及び貴金属めっき皮膜は、導電部材の用途に応じて、金属製基材の表裏両面に設けるようにしてもよく、片側面にのみ設けるようにしてもよい。 In the present invention, the means for forming the Ni plating film and the noble metal plating film may be an electroplating process or an electroless plating process, respectively. From the standpoint of superiority, it is preferable that both are formed by electroless plating. Further, the Ni plating film and the noble metal plating film may be provided on both the front and back surfaces of the metal base material according to the use of the conductive member, or may be provided only on one side surface.
　また、本発明において、金属製基材としては、例えば、銅又は真鍮などの銅合金、アルミニウム又はアルミニウム合金、鉄、ステンレス等の鉄合金等の基材を挙げることができるが、軽量であって加工性に優れ、電気伝導性・熱伝導性が高く、比較的安価であるなどの観点から、好ましくは、アルミニウム又はアルミニウム合金からなるアルミ基材であるのがよい。加えて、前述のＮｉめっき皮膜及び貴金属めっき皮膜が基材の片側表面にのみ形成される片面めっきである場合には、下記に示す各金属の標準酸化還元電位Ｅ0（25℃）から分るように、アルミ基材であれば、例えば燃料電池の使用時のような湿潤雰囲気に晒されても、Ａｌが最も卑な金属となるため、めっきを行わない裏面の裸の状態のＡｌが優先的に酸化される。つまり、仮に、貴金属めっき皮膜を通じてＮｉめっき皮膜が酸化雰囲気に晒されることがあっても、Ａｌが犠牲陽極として働くため、Ｎｉめっき皮膜に対しては電子が供給されて、Ｎｉめっき皮膜の酸化が抑制される。
　　　Au3+ + 3e- ⇔ Au  E0=1.50 V
　　　Pd2+ + 2e- ⇔ Pd  E0=0.99 V
　　　Cu2+ + 2e- ⇔ Cu  E0=0.34 V
　　　Ni2+ + 2e- ⇔ Ni  E0=-0.23 V
　　　Al3+ + 3e- ⇔ Al  E0=-1.66 V In the present invention, examples of the metal base material include base materials such as copper alloys such as copper or brass, aluminum or aluminum alloys, iron alloys such as iron and stainless steel, etc. From the viewpoints of excellent workability, high electrical and thermal conductivity, and relatively low cost, an aluminum substrate made of aluminum or an aluminum alloy is preferable. In addition, when the above-mentioned Ni plating film and noble metal plating film are single-sided plating formed only on one side surface of the substrate, it is found from the standard oxidation-reduction potential E 0 (25 ° C.) of each metal shown below. Thus, if it is an aluminum base, even if it is exposed to a moist atmosphere such as when a fuel cell is used, Al becomes the most basic metal, so the bare aluminum on the back surface without plating is preferred. Oxidized. In other words, even if the Ni plating film is exposed to the oxidizing atmosphere through the noble metal plating film, since Al works as a sacrificial anode, electrons are supplied to the Ni plating film, and the Ni plating film is oxidized. It is suppressed.
Au 3+ + 3e - ⇔ Au E 0 = 1.50 V
Pd 2+ + 2e - ⇔ Pd E 0 = 0.99 V
Cu 2+ + 2e - ⇔ Cu E 0 = 0.34 V
Ni 2+ + 2e - ⇔ Ni E 0 = -0.23 V
Al 3+ + 3e - ⇔ Al E 0 = -1.66 V
　ここで、アルミ基材に用いるアルミニウム又はアルミニウム合金については、特に制限されないが、例えば、高純度アルミニウム（JIS H4170; 1N99）や、Ａ１１００、Ａ３００３、Ａ５０５２、Ａ５００５、Ａ５６５２、Ａ６０６３、Ａ６０６１、Ａ６１０１、ＡＡ５２５２等の種々のアルミニウム合金を挙げることができる。なかでも、耐食性、成形性、強度、コストの観点から、５０００系のアルミニウム合金が好適である。 Here, the aluminum or aluminum alloy used for the aluminum substrate is not particularly limited. And various aluminum alloys. Among these, a 5000 series aluminum alloy is preferable from the viewpoint of corrosion resistance, formability, strength, and cost.
　また、アルミ基材を用いる場合には、Ｎｉめっき皮膜の形成に先駆けて、アルミ基材を亜鉛浸漬浴に浸漬して亜鉛置換処理を行い、Ｎｉめっき皮膜がアルミ基材上に形成された置換亜鉛層を介して形成されるようにするのがよい。ここで、亜鉛浸漬浴としては、例えば、酸化亜鉛４．１質量％、及び水酸化ナトリウム２５質量％等を含有する酸化亜鉛アルカリ水溶液をイオン交換水で４００ｍｌ／Ｌに希釈して用いることができ、浸漬温度は１５～３０℃程度、浸漬時間は１０秒～３分程度である。また、より緻密な置換亜鉛層を形成する目的から、亜鉛浸漬浴に浸漬してアルミ基材の表面に一旦置換亜鉛層を形成した後、酸洗浴に浸漬してこの置換亜鉛層を除去し、再び亜鉛浸漬浴に浸漬して置換亜鉛層を形成するようにしてもよい。その際の酸洗浴としては、例えば、酸が硝酸、硫酸、塩酸等であって濃度が１０～６５質量％の酸水溶液を用いることができ、浸漬温度は１５～３０℃程度、浸漬時間は１０秒～１分程度である。 In addition, when using an aluminum base, prior to the formation of the Ni plating film, the aluminum base is immersed in a zinc immersion bath to perform zinc replacement treatment, and the Ni plating film is formed on the aluminum base. It is good to form through a zinc layer. Here, as the zinc immersion bath, for example, an aqueous zinc oxide solution containing 4.1% by mass of zinc oxide and 25% by mass of sodium hydroxide can be diluted with ion-exchanged water to 400 ml / L and used. The immersion temperature is about 15 to 30 ° C., and the immersion time is about 10 seconds to 3 minutes. In addition, for the purpose of forming a denser substituted zinc layer, after forming a substituted zinc layer on the surface of the aluminum base by immersing in a zinc immersion bath, the immersion zinc bath is removed by immersing in a pickling bath, The substituted zinc layer may be formed by dipping in a zinc immersion bath again. As the pickling bath at that time, for example, an acid aqueous solution having an acid of nitric acid, sulfuric acid, hydrochloric acid or the like and having a concentration of 10 to 65 mass% can be used, the immersion temperature is about 15 to 30 ° C., and the immersion time is 10 Seconds to about 1 minute.
　また、亜鉛置換処理の前に脱脂処理やデスマット処理等を行って公知の方法でアルミ基材を前処理したり、プレス加工によってアルミ基材に接続端子等を形成するなど、所定の前処理加工を行うようにしてもよい。そして、貴金属めっき皮膜を形成した後には、水洗して乾燥させるなどして、本発明に係る導電部材を得ることができる。 In addition, a predetermined pretreatment process such as degreasing or desmut treatment prior to the zinc replacement treatment to pretreat the aluminum substrate by a known method, or forming a connection terminal or the like on the aluminum substrate by pressing. May be performed. After the noble metal plating film is formed, the conductive member according to the present invention can be obtained by washing with water and drying.
　本発明の導電部材は、耐食性に優れて、かつ、長期にわたって使用しても接触抵抗の増加を抑えることができる。そのため、燃料電池をはじめ、例えば、リードフレームやバスバー、プリント配線基板、接続端子等、種々の導電部材として利用することができる。特に、高温高湿度環境下でもＮｉの拡散を防ぐことができることから、燃料電池を形成する導電部材に適しており、なかでも集電板を形成するものとして好適である。 The conductive member of the present invention is excellent in corrosion resistance and can suppress an increase in contact resistance even when used for a long time. Therefore, it can be used as various conductive members such as fuel cells, lead frames, bus bars, printed wiring boards, connection terminals, and the like. In particular, since Ni can be prevented from diffusing even in a high-temperature and high-humidity environment, it is suitable as a conductive member for forming a fuel cell, and particularly suitable for forming a current collector plate.
　本発明によれば、特にＡｕめっき皮膜を設けることなく、接触抵抗が低く導電性に優れ、かつ、耐食性及び長期耐久性に優れた導電部材とすることができる。そのため、本発明の導電部材は、コスト性と品質とを同時に満たすものであって、長期にわたって信頼性良く使用することができる。 According to the present invention, a conductive member having a low contact resistance and excellent conductivity and excellent corrosion resistance and long-term durability can be obtained without particularly providing an Au plating film. Therefore, the conductive member of the present invention satisfies both cost and quality at the same time, and can be used reliably over a long period of time.
図１は、実施例１で得られた試験用導電部材におけるＰｄめっき皮膜の電子線回折像である。FIG. 1 is an electron beam diffraction image of a Pd plating film in the test conductive member obtained in Example 1. 図２は、本発明の導電部材を説明するための断面模式図である。FIG. 2 is a schematic cross-sectional view for explaining the conductive member of the present invention. 図３は、実施例１で得られた試験用導電部材のＮｉめっき皮膜とＰｄめっき皮膜の断面の様子を示すＴＥＭ画像である（倍率9,900倍）。FIG. 3 is a TEM image showing the cross section of the Ni plating film and the Pd plating film of the conductive member for test obtained in Example 1 (magnification 9,900 times). 図４は、実施例１で得られた試験用導電部材におけるＰｄめっき皮膜の断面の様子を示すＴＥＭ画像である（倍率285,000倍）。FIG. 4 is a TEM image showing the state of the cross section of the Pd plating film in the test conductive member obtained in Example 1 (magnification: 285,000 times). 図５は、試験用導電部材の接触抵抗を測定する様子を説明する模式図〔（ａ）側面図、（ｂ）斜視図〕である。FIG. 5 is a schematic diagram ((a) side view, (b) perspective view) illustrating how the contact resistance of the test conductive member is measured. 図６は、実施例３で得られた試験用導電部材におけるＰｄめっき皮膜の電子線回折像である。FIG. 6 is an electron diffraction image of a Pd plating film in the test conductive member obtained in Example 3. 図７は、実施例３で得られた試験用導電部材のＮｉめっき皮膜とＰｄめっき皮膜の断面の様子を示すＴＥＭ画像である（倍率9,900倍）。FIG. 7 is a TEM image showing a cross-sectional state of the Ni plating film and the Pd plating film of the test conductive member obtained in Example 3 (magnification 9,900 times). 図８は、実施例３で得られた試験用導電部材におけるＰｄめっき皮膜の断面の様子を示すＴＥＭ画像である（倍率285,000倍）。FIG. 8 is a TEM image showing the cross-sectional state of the Pd plating film in the test conductive member obtained in Example 3 (magnification: 285,000 times). 図９は、実施例４で得られた試験用導電部材におけるＲｕめっき皮膜の電子線回折像である。FIG. 9 is an electron diffraction image of the Ru plating film in the test conductive member obtained in Example 4. 図１０は、実施例４で得られた試験用導電部材のＮｉめっき皮膜とＲｕめっき皮膜の断面の様子を示すＴＥＭ画像である（倍率9,900倍）。FIG. 10 is a TEM image showing a cross-sectional state of the Ni plating film and the Ru plating film of the test conductive member obtained in Example 4 (magnification 9,900 times). 図１１は、実施例４で得られた試験用導電部材におけるＲｕめっき皮膜の断面の様子を示すＴＥＭ画像である（倍率285,000倍）。FIG. 11 is a TEM image showing the state of the cross section of the Ru plating film on the test conductive member obtained in Example 4 (magnification: 285,000 times). 図１２は、比較例２で得られた試験用導電部材におけるＰｄめっき皮膜の電子線回折像である。12 is an electron diffraction image of a Pd plating film in the test conductive member obtained in Comparative Example 2. FIG. 図１３は、比較例２で得られた試験用導電部材のＮｉめっき皮膜とＰｄめっき皮膜の断面の様子を示すＴＥＭ画像である（倍率9,900倍）。FIG. 13 is a TEM image showing the cross section of the Ni plating film and the Pd plating film of the conductive member for test obtained in Comparative Example 2 (magnification 9,900 times). 図１４は、比較例２で得られた試験用導電部材におけるＰｄめっき皮膜の断面の様子を示すＴＥＭ画像である（倍率285,000倍）。FIG. 14 is a TEM image showing a cross-sectional state of the Pd plating film in the test conductive member obtained in Comparative Example 2 (magnification: 285,000 times).
　以下、実施例及び比較例に基づいて本発明の好適な実施の形態を具体的に説明する。なお、これらの実施例及び比較例において、得られた各めっき皮膜の分析や結晶性の判定、及び試験用導電部材の各種物性については、それぞれ後述する方法で評価した。表１には結果をまとめて示している。 Hereinafter, preferred embodiments of the present invention will be described in detail based on examples and comparative examples. In these examples and comparative examples, analysis of each obtained plating film, determination of crystallinity, and various physical properties of the test conductive member were evaluated by methods described later. Table 1 summarizes the results.
（実施例１）
［試験用導電部材の作製］
　板厚３ｍｍのアルミニウム合金Ａ５０５２－Ｈ３４材から３０ｍｍ×６０ｍｍ×厚み３ｍｍの大きさのアルミ基材を切り出し、弱アルカリ性脱脂剤（奥野製薬工業社製商品名：トップアルクリーン161）を濃度３０ｇ／Ｌに希釈した水溶液に浸漬させて、５５℃で５分間の脱脂洗浄を行った。水洗後、水酸化ナトリウム３５質量％を含むエッチング剤（奥野製薬工業社製商品名：トップアルソフト108）を濃度５０ｇ／Ｌに希釈した水溶液に浸漬させて、５５℃で３０秒間のエッチングを行った。次いで、水洗した後、硝酸を含むデスマット液（奥野製薬工業社製商品名：トップデスマットN-20）を濃度１００ｍｌ／Ｌに希釈した水溶液に浸漬させて、２５℃で１分間のデスマット処理を行った。 (Example 1)
[Preparation of conductive member for test]
A 30 mm x 60 mm x 3 mm thick aluminum base material was cut out from a 3 mm thick aluminum alloy A5052-H34 material, and a weak alkaline degreasing agent (trade name: Top Alclean 161, manufactured by Okuno Pharmaceutical Co., Ltd.) at a concentration of 30 g / L. The sample was dipped in an aqueous solution diluted to 5 and degreased and washed at 55 ° C. for 5 minutes. After washing with water, an etching agent containing 35% by mass of sodium hydroxide (Okuno Pharmaceutical Co., Ltd., trade name: Top Alsoft 108) is immersed in an aqueous solution diluted to a concentration of 50 g / L, and etched at 55 ° C. for 30 seconds. It was. Next, after washing with water, a desmut solution containing nitric acid (trade name: Top Desmatt N-20, manufactured by Okuno Pharmaceutical Co., Ltd.) is immersed in an aqueous solution diluted to a concentration of 100 ml / L, and desmutted at 25 ° C. for 1 minute. went.
　次いで、水洗した後にアルミ基材の片側表面及び外周端面をマスクし、水酸化ナトリウム２０質量％、及び酸化亜鉛３．６質量％を含有する亜鉛処理液（奥野製薬工業社製商品名：サブスターZn-111）を濃度５００ｍｌ／Ｌに希釈した亜鉛浸漬浴を用いて、上記アルミ基材を２２℃で３０秒間浸漬させた。水洗後、濃度６２質量％の硝酸水溶液を酸洗浴として、アルミ基材を２５℃で３０秒間浸漬して、一旦アルミ基材の表面に形成された置換亜鉛層を剥離した。水洗後、再び上記亜鉛浸漬浴を用いて、２２℃で３０秒間アルミ基材を浸漬させておよそ１μｍの置換亜鉛層を形成するようにして、亜鉛置換処理を行った。 Next, after rinsing with water, one side surface and outer peripheral end surface of the aluminum base material are masked, and a zinc treatment solution containing 20% by mass of sodium hydroxide and 3.6% by mass of zinc oxide (trade name: Substar, manufactured by Okuno Pharmaceutical Co., Ltd.) The aluminum substrate was immersed for 30 seconds at 22 ° C. using a zinc immersion bath in which Zn-111) was diluted to a concentration of 500 ml / L. After washing with water, an aqueous solution of nitric acid having a concentration of 62% by mass was used as a pickling bath, and the aluminum substrate was immersed for 30 seconds at 25 ° C., and the substituted zinc layer once formed on the surface of the aluminum substrate was peeled off. After washing with water, using the zinc immersion bath again, the aluminum substrate was immersed at 22 ° C. for 30 seconds to form a substituted zinc layer of about 1 μm, and a zinc replacement treatment was performed.
　次いで、水洗した後、次亜リン酸ナトリウム１９質量％及び酢酸３．９質量％を含んだ薬剤（奥野製薬工業社製商品名：トップニコロンRCH-MLF）と、硫酸ニッケル３６質量％を含有したＮｉめっき液（同社製商品名：トップニコロンRCH-1LF）とを、それぞれ濃度１３０ｍｌ／Ｌと４０ｍｌ／Ｌとなるように水で希釈して混合したＮｉめっき浴を用いて、９０℃で３５分間浸漬させる無電解Ｎｉめっき処理を行った。これにより、マスクした面と反対側のアルミ基材の片側表面に膜厚４．７μｍのＮｉめっき皮膜が形成された。また、後述するめっき皮膜の分析評価及び結晶性判定によれば、このＮｉめっき皮膜はＰ元素換算でリン（Ｐ）を１１質量％含有しており、結晶組織は非晶質であった。 Next, after washing with water, a drug containing 19% by mass of sodium hypophosphite and 3.9% by mass of acetic acid (trade name: Top Nicolon RCH-MLF manufactured by Okuno Pharmaceutical Co., Ltd.) and 36% by mass of nickel sulfate are contained. The Ni plating solution (trade name: Top Nicolon RCH-1LF, manufactured by the same company) was diluted at 90 ° C. with a Ni plating bath that was diluted with water to a concentration of 130 ml / L and 40 ml / L, respectively. An electroless Ni plating treatment for immersion for 35 minutes was performed. As a result, a Ni plating film having a film thickness of 4.7 μm was formed on one surface of the aluminum base opposite to the masked surface. Moreover, according to the analysis evaluation and crystallinity determination of the plating film mentioned later, this Ni plating film contained 11 mass% of phosphorus (P) in terms of P element, and the crystal structure was amorphous.
　上記でＮｉめっき皮膜を形成して水洗した後、３５質量％塩酸に２５℃で３０秒浸漬してプリディップした。さらに１８質量％の塩酸と０．０４質量％のパラジウム塩を含有した薬剤（奥野製薬工業社製商品名：ＩＣＰアクセラ）を２００ml/Lとなるように水で希釈した触媒浴に３０℃で１分浸漬した。水洗後、錯化剤１３質量％を含んだ薬剤（奥野製薬工業社製商品名：トップパラスPDP-M）と、パラジウム塩を７．２質量％、錯化剤を５．６質量％含有した薬剤（同社製商品名：トップパラスPDP-A）と、リン酸塩を４１質量％含んだ薬剤（同社製商品名：トップパラスPDP-B）と、水酸化ナトリウムを７質量％、錯化剤を０．２９質量％含んだ薬剤（同社製商品名：トップパラスPDP-C）と、リン酸塩を４４質量％含んだ薬剤（同社製商品名：トップパラスPDP-D）と、エチレンジアミンを１７質量％、錯化剤を１６質量％、含硫黄化合物を０．１質量％含んだ薬剤（同社製商品名：トップパラスPDP-E）とを、それぞれ濃度２００ｍｌ／Ｌ、１２ｍｌ／Ｌ、７０ｍｌ／Ｌ、３０ｍｌ／Ｌ、３．５ｍｌ／Ｌ、１００ｍｌ／Ｌとなるように水で希釈してこれらを混ぜたＰｄめっき浴を用いて、５７℃で８分間浸漬させる無電解Ｐｄめっき処理を行った。これにより、Ｎｉめっき皮膜の上に膜厚４９ｎｍのＰｄめっき皮膜（貴金属めっき皮膜）が形成された。また、後述するめっき皮膜の分析評価及び結晶性判定によれば、このＰｄめっき皮膜はＰ元素換算でリン（Ｐ）を２質量％含有しており、結晶組織は非晶質であった。図１には、このＰｄめっき皮膜で得られたＴＥＭの電子線回折像（ハローパターン）が示されている。 After forming the Ni plating film and washing with water as described above, it was immersed in 35% by mass hydrochloric acid at 25 ° C. for 30 seconds and pre-dipped. Further, a drug containing 18% by mass of hydrochloric acid and 0.04% by mass of palladium salt (trade name: ICP Axela manufactured by Okuno Seiyaku Kogyo Co., Ltd.) was diluted with water so as to be 200 ml / L. Dipped for a minute. After washing with water, a drug containing 13% by mass of a complexing agent (trade name: Top Paras PDP-M manufactured by Okuno Pharmaceutical Co., Ltd.), 7.2% by mass of a palladium salt, and 5.6% by mass of a complexing agent were contained. Drug (product name: Topparas PDP-A), drug containing 41% by mass of phosphate (Product name: Topparas PDP-B), sodium hydroxide 7% by mass, complexing agent Containing 0.29% by mass (trade name: Top Palas PDP-C), 44% by mass of phosphate (trade name: Top Paras PDP-D), and 17 ethylenediamine. A drug containing 16% by mass, 16% by mass of a complexing agent, and 0.1% by mass of a sulfur-containing compound (trade name: Top Paras PDP-E manufactured by the same company), respectively, at concentrations of 200 ml / L, 12 ml / L, and 70 ml / L, 30ml / L, 3.5ml / L, 100ml / L Using Pd plating bath mixed with, subjected to electroless Pd plating process of dipping 8 minutes at 57 ° C.. As a result, a Pd plating film (noble metal plating film) having a film thickness of 49 nm was formed on the Ni plating film. Moreover, according to the analysis evaluation and crystallinity determination of the plating film mentioned later, this Pd plating film contained 2 mass% of phosphorus (P) in terms of P element, and the crystal structure was amorphous. FIG. 1 shows an electron beam diffraction image (halo pattern) of TEM obtained with this Pd plating film.
　そして、無電解Ｐｄめっき処理後に水洗し、湯洗してさらに乾燥させることで、図２に示したように、アルミ基材２の片側表面に置換亜鉛層３を介してＮｉめっき皮膜４、及びＰｄめっき皮膜５を備えた実施例１に係る試験用導電部材１を得た。なお、上記の各工程で用いためっき浴等の処理液量は全て２Ｌとして行った。 Then, after the electroless Pd plating treatment, it is washed with water, washed with hot water, and further dried, so that, as shown in FIG. A test conductive member 1 according to Example 1 provided with a Pd plating film 5 was obtained. In addition, all the amount of process liquids, such as a plating bath used at said each process, were performed as 2L.
　図３には、この実施例１で得られた試験用導電部材１について、透過型電子顕微鏡（TEM）による断面観察を行った結果を示している（倍率9,900倍）。ここでは、Ｐｄめっき皮膜５の表面に樹脂の保護膜を形成した後、ＦＩＢ（集束イオンビーム）法で薄片にしてＮｉめっき皮膜とＰｄめっき皮膜の断面を観察した。この断面画像観察からも確認されるように、Ｎｉめっき皮膜及びＰｄめっき皮膜は、いずれも均一な色調を有しており、非晶質であることが伺える。また、図４は、Ｐｄめっき皮膜の断面を285,000倍で観察したＴＥＭ画像である。このＴＥＭ画像では明確な結晶格子は確認されず、やはりＰｄめっき皮膜は非晶質であることが伺える。 FIG. 3 shows the result of cross-sectional observation with a transmission electron microscope (TEM) of the test conductive member 1 obtained in Example 1 (9,900 times magnification). Here, after forming a protective film of resin on the surface of the Pd plating film 5, it was made into a thin piece by FIB (focused ion beam) method, and the cross sections of the Ni plating film and the Pd plating film were observed. As confirmed from this cross-sectional image observation, it can be seen that both the Ni plating film and the Pd plating film have a uniform color tone and are amorphous. FIG. 4 is a TEM image obtained by observing the cross section of the Pd plating film at 285,000 times. In this TEM image, a clear crystal lattice is not confirmed, and it can be seen that the Pd plating film is amorphous.
［めっき皮膜の分析評価］
　ここで、上記で得られた試験用導電部材１におけるＮｉめっき皮膜、及び貴金属めっき皮膜の各膜厚測定は、それぞれ蛍光Ｘ線膜厚計（フィッシャー・インストゥルメンツ社製 フィッシャースコープXDVμ）を用いて行った。
　また、Ｎｉめっき皮膜中のリン（Ｐ）含有率の測定は、上記で使用したものと同じＮｉめっき浴を用意してＣｕ板上に析出させ（重元素であるＣｕのほうがＡｌより蛍光Ｘ線を散乱しやすいため）、蛍光Ｘ線装置（リガク社製 RIX2100）により測定し、ＦＰ法（ファンダメンタル・パラメータ法）でＰ含有率の定量分析を行って求めた。一方、貴金属めっき皮膜中のリン（Ｐ）含有率の測定では、Ｃｕ板上にＢを含有したＮｉめっき（Ni-Bめっき）を析出させた上で、上記で使用したものと同じＰｄめっき浴を用いてＰｄめっきを析出させて、Ｎｉめっき皮膜の場合と同様に蛍光Ｘ線装置によるＦＰ法でＰ含有率を定量分析した。但し、後述する実施例４については、ＥＰＭＡによるＦＰ法により塩化ルテニウム由来のＣｌ元素含有率を定量分析した。 [Analysis and evaluation of plating film]
Here, each film thickness measurement of the Ni plating film and the noble metal plating film in the test conductive member 1 obtained above was performed using a fluorescent X-ray film thickness meter (Fischer Scope XDVμ manufactured by Fischer Instruments). I went.
In addition, the phosphorus (P) content in the Ni plating film is measured by preparing the same Ni plating bath as used above and precipitating it on a Cu plate (Cu, which is a heavy element, is more fluorescent X-ray than Al). It was measured with a fluorescent X-ray apparatus (RIX2100, manufactured by Rigaku Corporation), and the P content was quantitatively analyzed by the FP method (fundamental parameter method). On the other hand, in the measurement of the phosphorus (P) content in the noble metal plating film, Ni plating containing Ni (Ni-B plating) was deposited on a Cu plate, and then the same Pd plating bath as used above The Pd plating was deposited using, and the P content was quantitatively analyzed by the FP method using a fluorescent X-ray apparatus in the same manner as in the case of the Ni plating film. However, about Example 4 mentioned later, Cl element content rate derived from ruthenium chloride was quantitatively analyzed by FP method by EPMA.
［めっき皮膜の結晶性判定］
　また、試験用導電部材１におけるＮｉめっき皮膜、及び貴金属めっき皮膜の結晶性を判定するにあたり、ＦＥＩ製Ｑｕａｎｔａ ３Ｄ型集束イオンビーム加工装置（FIB)により、試験用導電部材１の断面（めっきサンプル断面）にカーボン保護膜を付けてから、観察部位を摘出し、銅メッシュに固定させ、厚さ１００ｎｍに薄膜加工したものを観察試料とした。そして、ＦＥＩ製Ｔｅｃｎａｉ Ｇ２ Ｆ２０ Ｓ－ＴＷＩＮ透過電子顕微鏡（TEM）により、加速電圧２００ｋＶの条件で観察及び画像取得を行った。ＴＥＭ観察に用いた貴金属めっき皮膜は、膜厚が約１００ｎｍであったため、直径２００ｎｍのアパーチャーを用いて電子線回折領域を制限し、目的の場所のみの電子線回折画像（制限視野電子線回折像）が得られるように観察条件を調整した。そして、各めっき皮膜について、得られた電子線回折画像に格子点が明りょうに確認された場合は結晶質、格子点が不明りょうの場合は微結晶質、及び、格子点はなく、ハローパターンが確認された場合は非晶質と判定した。 [Crystallinity determination of plating film]
Further, in determining the crystallinity of the Ni plating film and the noble metal plating film in the test conductive member 1, the cross section of the test conductive member 1 (cross section of the plating sample) was measured by the FEI Quanta 3D type focused ion beam processing apparatus (FIB). ) Was attached with a carbon protective film, the observation site was extracted, fixed to a copper mesh, and processed into a thin film with a thickness of 100 nm as an observation sample. Then, observation and image acquisition were performed with a Tecnai G2 F20 S-TWIN transmission electron microscope (TEM) manufactured by FEI under the condition of an acceleration voltage of 200 kV. Since the noble metal plating film used for TEM observation had a film thickness of about 100 nm, the electron diffraction region was limited using an aperture having a diameter of 200 nm, and an electron diffraction image (limited field electron diffraction image) of only the target location. The observation conditions were adjusted so that For each plating film, when the lattice point is clearly confirmed in the obtained electron beam diffraction image, there is no crystallinity, and when the lattice point is unknown, there is no microcrystalline and lattice point, and the halo pattern is When confirmed, it was determined to be amorphous.
［接触抵抗測定］
　上記で得られた試験用導電部材について、以下のようにして接触抵抗を測定した。図５（ａ）に示したように、貴金属めっき皮膜側を比較板７に接触させてこれらを上板６と下板８の間に挟み込み、上下方向から面圧を掛けながら試験用導電部材１の接触抵抗値を測定した。一般に、燃料電池の集電板に求められる接触抵抗は、通常の使用態様を想定して面圧が１ＭＰａの場合に１０ｍΩ・ｃｍ2程度であるところ、上記で得られた試験用導電部材１は、面圧が１ＭＰａの場合の接触抵抗が約０．０５ｍΩ・ｃｍ2であって、極めて良好な接触抵抗を示すことが分った。なお、上板６、比較板７、及び下板８は、それぞれ３０ｍｍ×６０ｍｍ×厚み３ｍｍのアルミ板（A5052材）の表裏両面に膜厚５μｍのＮｉめっき皮膜を介して膜厚０．１μｍのＡｕめっき皮膜を有したものであり、図５（ｂ）に示したように、これらの縦横方向を交互に重ねた接触抵抗測定試料を準備し、試験用導電部材１と比較板７との接触面積Ｓは３ｍｍ×３ｍｍ＝９ｃｍ2とした。また、接触抵抗（mΩ・cm2）は、上板６と下板８との間に２Ａの電流Ｉを流して試験用導電部材１と比較板７との間の電圧Ｖを測定し、Ｒ（mΩ・cm2）＝Ｖ×Ｓ／Ｉ＝Ｖ×９／２から求めた。 [Contact resistance measurement]
For the test conductive member obtained above, the contact resistance was measured as follows. As shown in FIG. 5 (a), the noble metal plating film side is brought into contact with the comparison plate 7, and these are sandwiched between the upper plate 6 and the lower plate 8, and the test conductive member 1 is applied while applying a surface pressure from above and below. The contact resistance value of was measured. In general, the contact resistance required for the current collector plate of the fuel cell is about 10 mΩ · cm 2 when the surface pressure is 1 MPa assuming a normal use mode. It was found that the contact resistance when the surface pressure was 1 MPa was about 0.05 mΩ · cm 2 , indicating a very good contact resistance. The upper plate 6, the comparison plate 7, and the lower plate 8 each have a thickness of 0.1 μm via a Ni plating film having a thickness of 5 μm on both front and back surfaces of an aluminum plate (A5052 material) of 30 mm × 60 mm × thickness 3 mm. As shown in FIG. 5 (b), a contact resistance measurement sample in which the vertical and horizontal directions are alternately stacked is prepared, and the contact between the test conductive member 1 and the comparison plate 7 is prepared. The area S was 3 mm × 3 mm = 9 cm 2 . Further, the contact resistance (mΩ · cm 2 ) is measured by measuring the voltage V between the test conductive member 1 and the comparison plate 7 by passing a current I of 2 A between the upper plate 6 and the lower plate 8. (MΩ · cm 2 ) = V × S / I = V × 9/2.
［アノード分極試験］
　上記と同様にして得た試験用導電部材について、以下のようにしてアノード分極試験を行った。先ず、試験用導電部材をマスキングして電極面積１ｃｍ2を露出させて作用極（WE）とした。また、飽和カロメル電極（SCE)を参照極（RE）とし、白金を対極（CE)として、これらを５質量％硫酸水溶液（30℃）中に浸漬して、ポテンショスタット（北斗電工社製 HZ-3000）を用いて走引速度２０ｍＶ／ｍｉｎでアノード分極した。そして、得られた電流電位曲線において、電圧１Ｖのときのアノード電流を求めた。耐食性の良いめっき皮膜はアノード電流が低いことから、ここでは、１ｍＡ／ｃｍ２以下であれば〇、そうでなければ×と判定した。 [Anode polarization test]
An anodic polarization test was conducted on the test conductive member obtained in the same manner as described above as follows. First, the test conductive member was masked to expose an electrode area of 1 cm 2 to obtain a working electrode (WE). In addition, a saturated calomel electrode (SCE) is used as a reference electrode (RE), platinum is used as a counter electrode (CE), and these are immersed in a 5% by weight sulfuric acid aqueous solution (30 ° C) to obtain a potentiostat (HZ- 3000) and anodically polarized at a running speed of 20 mV / min. Then, in the obtained current-potential curve, the anode current at a voltage of 1 V was obtained. Since a plating film with good corrosion resistance has a low anode current, it was judged as ◯ if it was 1 mA / cm 2 or less, and x otherwise.
［硝酸ばっ気試験］
　上記と同様にして得た試験用導電部材について、ＪＩＳ－Ｈ８６２０附属書１に従って硝酸ばっ気試験を行った。先ず、念のため貴金属めっき皮膜の表面の汚れをエタノールで除去し、乾燥させた後、容積２Ｌのデシケーターの底部に５ｍｌの硝酸を入れ、磁製板の上に得られた試験用導電部材を載せて蓋をした。そして、約２３℃で１時間放置した後、試験用導電部材を取り出して静かに水洗して乾燥させた上で、目視にて腐食点の発生の有無を確認したところ、この実施例１に係る試験用導電部材では、腐食点は確認されなかった。なお、以降の実施例、比較例では、腐食点の存在する箇所が試験用導電部材の１ｃｍ2あたりで５か所未満であれば〇、５か所以上であれば×と判定した。 [Nitric acid aeration test]
The test conductive member obtained in the same manner as described above was subjected to a nitrate aeration test in accordance with JIS-H8620 Annex 1. First, as a precaution, the dirt on the surface of the noble metal plating film is removed with ethanol and dried, and then 5 ml of nitric acid is added to the bottom of a desiccator having a volume of 2 L, and the test conductive member obtained on the magnetic plate is placed. Placed and covered. And after leaving at about 23 degreeC for 1 hour, after taking out the electrically conductive member for a test, washing with water gently and drying, when the presence or absence of the generation | occurrence | production of a corrosion point was confirmed visually, it concerns on this Example 1. In the test conductive member, no corrosion point was confirmed. In the following examples and comparative examples, it was determined that the location where the corrosion point was present was less than 5 per 1 cm 2 of the test conductive member, and that the location was 5 if it was 5 or more.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
（実施例２）
　Ｐｄめっき浴への浸漬時間を１４分間にして無電解Ｐｄめっき処理を行った以外は実施例１と同様にして、実施例２に係る試験用導電部材を得た。得られた試験用導電部材は、リン含有量が１１質量％であって膜厚５．２μｍのＮｉめっき皮膜を備えると共に、リン含有量が２質量％であって膜厚８７ｎｍのＰｄめっき皮膜を備えており、いずれのめっき皮膜も結晶組織は非晶質であった。この実施例２に係る試験用導電部材について、実施例１と同様にして接触抵抗を測定したところ、面圧が１ＭＰａの場合の接触抵抗は実施例１と同程度であった。また、その他の評価についても実施例１と同様にして行った。結果を表１に示す。 (Example 2)
A test conductive member according to Example 2 was obtained in the same manner as in Example 1 except that the electroless Pd plating treatment was performed with the immersion time in the Pd plating bath being 14 minutes. The obtained conductive member for test was provided with a Ni plating film having a phosphorus content of 11% by mass and a film thickness of 5.2 μm, and a Pd plating film having a phosphorus content of 2% by mass and a film thickness of 87 nm. All the plating films were amorphous in crystal structure. When the contact resistance of the test conductive member according to Example 2 was measured in the same manner as in Example 1, the contact resistance when the surface pressure was 1 MPa was about the same as that in Example 1. Other evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
（実施例３）
　以下のようにして無電解Ｐｄめっき処理を行った以外は実施例１と同様にして、実施例３に係る試験用導電部材を得た。すなわち、この実施例３では、エチレンジアミンを２．５質量％、パラジウム塩を４．０質量％含有した薬剤（同社製商品名：ムデンノーブルPD-1）と、次亜リン酸塩を１１質量％含んだ薬剤（同社製商品名：ムデンノーブルPD-2）と、エチレンジアミンを２．１質量％、次亜リン酸塩を６．０質量％、錯化剤を５．４質量％含んだ薬剤（同社製商品名：ムデンノーブルPD-3）とを、それぞれ濃度５０ｍｌ／Ｌ、５０ｍｌ／Ｌ、１００ｍｌ／Ｌとなるように水で希釈してこれらを混ぜたＰｄめっき浴を用いて、５５℃で２分間浸漬させる無電解Ｐｄめっき処理を行った。 (Example 3)
A test conductive member according to Example 3 was obtained in the same manner as in Example 1 except that the electroless Pd plating treatment was performed as follows. That is, Example 3 contains 2.5% by mass of ethylenediamine and 4.0% by mass of a palladium salt (trade name: Muden Noble PD-1) and 11% by mass of hypophosphite. Drug (trade name: Muden Noble PD-2 made by the company), 2.1 mass% ethylenediamine, 6.0 mass% hypophosphite, and 5.4 mass% complexing agent (made by the company) Product name: Muden Noble PD-3) is immersed in water at 55 ° C. for 2 minutes using a Pd plating bath in which these are diluted with water to a concentration of 50 ml / L, 50 ml / L, and 100 ml / L and mixed with each other. An electroless Pd plating treatment was performed.
　これにより、実施例３に係る試験用導電部材では、リン含有量が１１質量％であって膜厚５．３μｍのＮｉめっき皮膜を備えると共に、リン含有量が５質量％であって膜厚５３ｎｍのＰｄめっき皮膜を備えており、いずれのめっき皮膜も結晶組織は非晶質であった。図６には、Ｐｄめっき皮膜で得られたＴＥＭの電子線回折像（ハローパターン）が示されている。また、この実施例３に係る試験用導電部材について、実施例１と同様にして接触抵抗を測定したところ、面圧が１ＭＰａの場合の接触抵抗は実施例１と同程度であった。また、その他の評価についても実施例１と同様にして行った。結果を表１に示す。 Thus, in the test conductive member according to Example 3, the phosphorus content was 11% by mass and the Ni plating film having a film thickness of 5.3 μm was provided, and the phosphorus content was 5% by mass and the film thickness was 53 nm. The Pd plating film was provided, and any of the plating films had an amorphous crystal structure. FIG. 6 shows an electron beam diffraction image (halo pattern) of TEM obtained with the Pd plating film. Further, when the contact resistance of the test conductive member according to Example 3 was measured in the same manner as in Example 1, the contact resistance when the surface pressure was 1 MPa was about the same as that in Example 1. Other evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
　また、得られた試験用導電部材について、透過型電子顕微鏡（TEM）による断面観察を行った（倍率9,900倍）。Ｐｄめっき皮膜の表面に樹脂の保護膜を形成した後、ＦＩＢ（集束イオンビーム）法で薄片にしてＮｉめっき皮膜とＰｄめっき皮膜の断面を観察した。結果を図７に示す。この断面画像の観察によっても、Ｎｉめっき皮膜、及びＰｄめっき皮膜には、それぞれ結晶粒界のようなものは確認されず、いずれも非晶質であることが分る。更に、図８は、Ｐｄめっき皮膜の断面を285,000倍で観察したＴＥＭ画像である。このＴＥＭ画像では明確な結晶格子は確認されず、やはりＰｄめっき皮膜は非晶質であることが伺える。 Further, the obtained conductive member for test was subjected to cross-sectional observation with a transmission electron microscope (TEM) (magnification 9,900 times). After forming a protective film of resin on the surface of the Pd plating film, it was made into a thin piece by FIB (focused ion beam) method, and cross sections of the Ni plating film and the Pd plating film were observed. The results are shown in FIG. Even by observing this cross-sectional image, it is found that neither the Ni-plated film nor the Pd-plated film is a crystal grain boundary, and both are amorphous. Further, FIG. 8 is a TEM image obtained by observing the cross section of the Pd plating film at 285,000 times. In this TEM image, a clear crystal lattice is not confirmed, and it can be seen that the Pd plating film is amorphous.
（実施例４）
　以下のようにしてルテニウム（Ｒｕ）めっき皮膜からなる貴金属めっき皮膜を形成した以外は実施例１と同様にして、実施例４に係る試験用導電部材を得た。すなわち、実施例１と同様にしてＮｉめっき皮膜を形成して水洗した後、脱脂剤（奥野製薬工業社製商品名：エースクリーン801）を５０ｇ／Ｌとなるように水で希釈して作製した脱脂浴に５０℃で５分間浸漬させることで脱脂処理した。試験用導電部材を水洗した後、脱脂剤（奥野製薬工業社製商品名：トップクリーナーE）を５０ｍｌ／Ｌ、及び、水酸化ナトリウムを５０ｇ／Ｌとなるよう混合して水で希釈して作製した脱脂浴に室温で浸漬し、試験用導電部材に５Ａ／ｄｍ２のアノード電流を１分間通電する陽極電解脱脂処理を行った。更に水洗した後、３５質量％の塩酸を２００ｍｌ／Ｌとなるよう水で希釈した液に試験用導電部材を１分間浸漬し、導電部材表面を活性化した後に水洗を行い、更に塩化ルテニウムを２０ｇ／Ｌ含む７５℃のルテニウムめっき浴に浸漬し、１Ａ／ｄｍ２の電流を２分間通電することにより、電解Ｒｕめっき処理を行った。 Example 4
A test conductive member according to Example 4 was obtained in the same manner as in Example 1 except that a noble metal plating film composed of a ruthenium (Ru) plating film was formed as follows. That is, after the Ni plating film was formed and washed in the same manner as in Example 1, the degreasing agent (trade name: Okure Pharmaceutical Co., Ltd., trade name: A-screen 801) was diluted with water so as to be 50 g / L. Degreasing was performed by immersing in a degreasing bath at 50 ° C. for 5 minutes. Prepared by washing the test conductive member with water, mixing the degreasing agent (trade name: Top Cleaner E, manufactured by Okuno Seiyaku Kogyo Co., Ltd.) to 50 ml / L and sodium hydroxide to 50 g / L and diluting with water. An anodic electrolytic degreasing treatment was conducted in which the test conductive member was immersed in an anodic current of 5 A / dm 2 for 1 minute. After further washing with water, the conductive member for test was immersed in a solution diluted with 35% by weight of hydrochloric acid to 200 ml / L for 1 minute to activate the surface of the conductive member, followed by washing with water and 20 g of ruthenium chloride. Electrolytic Ru plating treatment was performed by immersing in a ruthenium plating bath containing 75 L / L and applying a current of 1 A / dm 2 for 2 minutes.
　これにより、この実施例４では、リン含有量が１１質量％であって膜厚５．６μｍのＮｉめっき皮膜を備えると共に、Ｃｌ含有量が２．５質量％であって膜厚９３ｎｍのＲｕめっき皮膜を備えた試験用導電部材が得られた。このうち、Ｎｉめっき皮膜の結晶組織は非晶質であり、一方のＲｕめっき皮膜の結晶組織は微結晶質であった。図９には、このＲｕめっき皮膜で得られたＴＥＭの電子線回折像（格子点が不明りょう）が示されている。 Thereby, in this Example 4, while containing a Ni plating film having a phosphorus content of 11% by mass and a film thickness of 5.6 μm, the Cl content is 2.5% by mass and the Ru plating having a film thickness of 93 nm. A test conductive member provided with a film was obtained. Among these, the crystal structure of the Ni plating film was amorphous, and the crystal structure of one Ru plating film was microcrystalline. FIG. 9 shows an electron beam diffraction image (having an unknown lattice point) of TEM obtained with this Ru plating film.
　この実施例４に係る試験用導電部材について、実施例１と同様にして接触抵抗を測定したところ、面圧が１ＭＰａの場合の接触抵抗は実施例１と同程度であった。また、その他の評価についても実施例１と同様にして行った。結果を表１に示す。 For the test conductive member according to Example 4, when the contact resistance was measured in the same manner as in Example 1, the contact resistance when the surface pressure was 1 MPa was about the same as in Example 1. Other evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
　また、得られた試験用導電部材について、透過型電子顕微鏡（TEM）による断面観察を行った（倍率9,900倍）。Ｒｕめっき皮膜の表面に樹脂の保護膜を形成した後、ＦＩＢ（集束イオンビーム）法で薄片にしてＮｉめっき皮膜とＲｕめっき皮膜の断面を観察した。結果を図１０に示す。この断面画像の観察によれば、実施例１や実施例３のＰｄめっき皮膜に比べて、Ｒｕめっき皮膜は結晶の粒界に起因する色の濃淡がわずかに確認できる。一方、図１１は、Ｒｕめっき皮膜の断面を285,000倍で観察したＴＥＭ画像である。これによれば、電解めっき処理で形成されたＲｕめっき皮膜は、結晶格子のドメインが５～１０ｎｍ程度の微結晶で構成されていることが確認できる。 Further, the obtained conductive member for test was subjected to cross-sectional observation with a transmission electron microscope (TEM) (magnification 9,900 times). After a resin protective film was formed on the surface of the Ru plating film, the cross section of the Ni plating film and the Ru plating film was observed using a FIB (focused ion beam) method. The results are shown in FIG. According to the observation of the cross-sectional image, compared to the Pd plating films of Example 1 and Example 3, the Ru plating film can slightly confirm the color shade caused by the crystal grain boundaries. On the other hand, FIG. 11 is a TEM image obtained by observing the cross section of the Ru plating film at 285,000 times. According to this, it can be confirmed that the Ru plating film formed by the electrolytic plating treatment is composed of microcrystals having a crystal lattice domain of about 5 to 10 nm.
（比較例１）
　以下のようにして無電解Ｎｉめっき処理を行うと共に、Ｐｄめっき浴の浴温度を５７℃、浸漬時間を８分間にして無電解Ｐｄめっき処理を行った以外は実施例１と同様にして、比較例１に係る試験用導電部材を得た。すなわち、この比較例１では、次亜リン酸ナトリウム１１質量％及び錯化剤２４質量％を含んだ薬剤（奥野製薬工業社製商品名：ICPニコロンGSR-M）と、硫酸ニッケル３６質量％を含有したＮｉめっき液（同社製商品名：ICPニコロンGSR-1）とを、それぞれ濃度１５０ｍｌ／Ｌと５０ｍｌ／Ｌとなるように水で希釈して混合したＮｉめっき浴を用いて、８０℃で３０分間浸漬させる無電解Ｎｉめっき処理を行った。 (Comparative Example 1)
In the same manner as in Example 1 except that the electroless Ni plating treatment was performed as follows, and the bath temperature of the Pd plating bath was 57 ° C. and the immersion time was 8 minutes, the electroless Pd plating treatment was performed. A test conductive member according to Example 1 was obtained. That is, in this Comparative Example 1, a drug containing 11% by mass of sodium hypophosphite and 24% by mass of a complexing agent (trade name: ICP Nicolon GSR-M manufactured by Okuno Pharmaceutical Co., Ltd.) and 36% by mass of nickel sulfate were added. The Ni plating solution contained (trade name: ICP Nicolon GSR-1 manufactured by the company) was diluted at 80 ° C. with a Ni plating bath that was diluted with water to a concentration of 150 ml / L and 50 ml / L, respectively. An electroless Ni plating treatment for immersion for 30 minutes was performed.
　これにより、比較例１に係る試験用導電部材では、リン含有量が６質量％であって膜厚５．１μｍのＮｉめっき皮膜を備えると共に、リン含有量が２質量％であって膜厚５２ｎｍのＰｄめっき皮膜を備えていた。このうち、Ｎｉめっき皮膜の結晶組織は結晶質であり、また、Ｐｄめっき皮膜の結晶組織は非晶質であった。そして、この比較例１に係る試験用導電部材について、実施例１と同様に各種評価を行った。その結果、接触抵抗については良好な値を示したものの、表１に示したように、耐食性や耐久性に関する評価はいずれも満足できるものではなかった。 Thus, in the test conductive member according to Comparative Example 1, the phosphorus content was 6% by mass and the Ni plating film having a film thickness of 5.1 μm was provided, and the phosphorus content was 2% by mass and the film thickness was 52 nm. The Pd plating film was provided. Among these, the crystal structure of the Ni plating film was crystalline, and the crystal structure of the Pd plating film was amorphous. The test conductive member according to Comparative Example 1 was evaluated in the same manner as in Example 1. As a result, although the contact resistance showed a good value, as shown in Table 1, none of the evaluations regarding corrosion resistance and durability were satisfactory.
（比較例２）
　以下のようにして無電解Ｐｄめっき処理を行った以外は実施例１と同様にして、比較例２に係る試験用導電部材を得た。すなわち、この比較例２では、キレート剤を含んだ薬剤（奥野製薬工業社製商品名：パラトップLP-M）と、パラジウム塩を７質量％含有した薬剤（同社製商品名：パラトップLP-A）と、還元剤を４１質量％含んだ薬剤（同社製商品名：パラトップLP－B）と、錯化剤を４．４質量％含んだ薬剤（同社製商品名：パラトップLP-C）とを、それぞれ濃度２００ｍｌ／Ｌ、２０ｍｌ／Ｌ、７０ｍｌ／Ｌ、１０ｍｌ／Ｌとなるように水で希釈してこれらを混ぜたＰｄめっき浴を用いて、６０℃で１０分間浸漬させる無電解Ｐｄめっき処理を行った。 (Comparative Example 2)
A test conductive member according to Comparative Example 2 was obtained in the same manner as in Example 1 except that the electroless Pd plating treatment was performed as follows. That is, in Comparative Example 2, a drug containing a chelating agent (trade name: Paratop LP-M manufactured by Okuno Pharmaceutical Co., Ltd.) and a drug containing 7% by mass of a palladium salt (trade name manufactured by the company: Paratop LP-) A), a drug containing 41% by mass of a reducing agent (trade name: Paratop LP-B) and a drug containing 4.4% by mass of a complexing agent (trade name: Paratop LP-C) ) Is immersed in water at 60 ° C. for 10 minutes using a Pd plating bath in which these are diluted with water to a concentration of 200 ml / L, 20 ml / L, 70 ml / L, and 10 ml / L, respectively. Pd plating treatment was performed.
　これにより、比較例２に係る試験用導電部材では、リン含有量が１１質量％であって膜厚５．６μｍのＮｉめっき皮膜を備えると共に、リン含有量が１質量％であって膜厚６３ｎｍのＰｄめっき皮膜を備えていた。このうち、Ｎｉめっき皮膜の結晶組織は非晶質であり、また、Ｐｄめっき皮膜の結晶組織は結晶質であった。図１２には、Ｐｄめっき皮膜で得られたＴＥＭの電子線回折像（格子点が明りょう）が示されている。そして、この比較例２に係る試験用導電部材について、実施例１と同様に各種評価を行った。その結果、接触抵抗については良好な値を示したものの、表１に示したように、耐食性や耐久性に関する評価はいずれも満足できるものではなかった。 Thus, in the test conductive member according to Comparative Example 2, the phosphorus content was 11% by mass and the Ni plating film having a film thickness of 5.6 μm was provided, and the phosphorus content was 1% by mass and the film thickness was 63 nm. The Pd plating film was provided. Among these, the crystal structure of the Ni plating film was amorphous, and the crystal structure of the Pd plating film was crystalline. FIG. 12 shows an electron beam diffraction image (clear lattice points) of TEM obtained with the Pd plating film. Various evaluations were performed on the test conductive member according to Comparative Example 2 in the same manner as in Example 1. As a result, although the contact resistance showed a good value, as shown in Table 1, none of the evaluations regarding corrosion resistance and durability were satisfactory.
　また、得られた試験用導電部材について、実施例と同様にして透過型電子顕微鏡（TEM）による断面観察を行った（倍率9,900倍）。結果は図１３に示したとおりであり、Ｐｄめっき皮膜には、結晶粒の粒界に起因する色の濃淡が確認され、結晶質を有することが伺える。更に、図１４は、Ｐｄめっき皮膜の断面を285,000倍で観察したＴＥＭ画像であり、数十ｎｍを超える結晶格子の縞模様のドメインが確認できる。 Further, the obtained conductive member for test was observed with a transmission electron microscope (TEM) in the same manner as in the example (magnification: 9,900 times). The result is as shown in FIG. 13, and the Pd plating film is confirmed to have color shading due to the grain boundaries of the crystal grains, and has a crystalline quality. Further, FIG. 14 is a TEM image obtained by observing a cross section of the Pd plating film at 285,000 times, and a domain of a stripe pattern of a crystal lattice exceeding several tens of nm can be confirmed.
　上記実施例及び比較例の結果から分かるように、本発明に係る実施例１～４の導電部材は、いずれも接触抵抗が小さく、耐食性及び長期耐久性に優れたものであった。それに対して、Ｎｉめっき皮膜のリン含有率が低い比較例１の場合や、Ｐｄめっき皮膜のリン含有率が低くて結晶質の結晶組織を有する比較例２の場合には、耐食性に劣り、硝酸ばっ気試験によっても腐食点が多数確認されたことから、長期の使用に耐え得るものではないと考えられる。 As can be seen from the results of the above Examples and Comparative Examples, all of the conductive members of Examples 1 to 4 according to the present invention had low contact resistance and excellent corrosion resistance and long-term durability. On the other hand, in the case of Comparative Example 1 in which the phosphorus content of the Ni plating film is low or in the case of Comparative Example 2 having a low phosphorus content of the Pd plating film and having a crystalline crystal structure, the corrosion resistance is poor. Since many corrosion spots were confirmed by the aeration test, it is not considered that it can withstand long-term use.
１：導電部材、２：アルミ基材、３：置換亜鉛層、４：Ｎｉめっき皮膜、５：Ｐｄめっき皮膜、６：上板、７：比較板、８：下板。 1: conductive member, 2: aluminum substrate, 3: substituted zinc layer, 4: Ni plating film, 5: Pd plating film, 6: upper plate, 7: comparison plate, 8: lower plate.

Claims (10)

  1. 　金属製基材の表面にＮｉめっき皮膜を介して貴金属めっき皮膜を備えた導電部材であって、前記Ｎｉめっき皮膜はリン（Ｐ）を１０質量％以上含み、また、前記貴金属めっき皮膜は、Ｐｄ、Ｐｔ、Ｒｈ、Ｉｒ、Ｏｓ、及びＲｕからなる群から選ばれたいずれか１以上の貴金属を含むと共に、非晶質又は微結晶質であり、かつ、膜厚が２０ｎｍ以上２００ｎｍ未満であることを特徴とする導電部材。 A conductive member provided with a noble metal plating film on a surface of a metal substrate through a Ni plating film, wherein the Ni plating film contains 10% by mass or more of phosphorus (P), and the noble metal plating film is made of Pd. , Pt, Rh, Ir, Os, and Ru, including at least one noble metal selected from the group consisting of amorphous, microcrystalline, and a film thickness of 20 nm or more and less than 200 nm A conductive member.
  2. 　前記貴金属めっき皮膜が、リン（Ｐ）、ホウ素（Ｂ）、及びタングステン（Ｗ）からなる群から選ばれたいずれか１以上の共析元素を２質量％以上含むものである請求項１に記載の導電部材。 2. The conductive material according to claim 1, wherein the noble metal plating film contains 2% by mass or more of any one or more eutectoid elements selected from the group consisting of phosphorus (P), boron (B), and tungsten (W). Element.
  3. 　前記Ｎｉめっき皮膜は、非晶質である請求項１又は２に記載の導電部材。 The conductive member according to claim 1, wherein the Ni plating film is amorphous.
  4. 　前記Ｎｉめっき皮膜及び貴金属めっき皮膜は、いずれも無電解めっき処理により形成されたものである請求項１～３のいずれかに記載の導電部材。 The conductive member according to any one of claims 1 to 3, wherein each of the Ni plating film and the noble metal plating film is formed by an electroless plating process.
  5. 　前記Ｎｉめっき皮膜は無電解めっき処理により形成され、前記貴金属めっき皮膜は電解めっき処理により形成されたものである請求項１～３のいずれかに記載の導電部材。 4. The conductive member according to claim 1, wherein the Ni plating film is formed by an electroless plating process, and the noble metal plating film is formed by an electrolytic plating process.
  6. 　前記Ｎｉめっき皮膜の膜厚が１μｍ以上１０μｍ以下である請求項１～５のいずれかに記載の導電部材。 The conductive member according to any one of claims 1 to 5, wherein the Ni plating film has a thickness of 1 µm or more and 10 µm or less.
  7. 　金属製基材が、アルミニウム又はアルミニウム合金からなるアルミ基材である請求項１～６のいずれかに記載の導電部材。 The conductive member according to any one of claims 1 to 6, wherein the metal substrate is an aluminum substrate made of aluminum or an aluminum alloy.
  8. 　前記Ｎｉめっき皮膜が、アルミ基材上に形成された置換亜鉛層を介して形成されている請求項７に記載の導電部材。 The conductive member according to claim 7, wherein the Ni plating film is formed through a substituted zinc layer formed on an aluminum base material.
  9. 　燃料電池単位セルが複数積層されたセル積層体の両端面に配設されて電流を取り出す燃料電池集電板に用いられるものである請求項１～８のいずれかに記載の導電部材。 The conductive member according to any one of claims 1 to 8, wherein the conductive member is used for a fuel cell current collector plate that is disposed on both end faces of a cell laminate in which a plurality of fuel cell unit cells are laminated to extract current.
  10. 　バスバーに用いられるものである請求項１～８のいずれかに記載の導電部材。 The conductive member according to any one of claims 1 to 8, which is used for a bus bar.
PCT/JP2014/066869 2013-06-28 2014-06-25 Conductive member WO2014208610A1 (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000087291A (en) * 1998-09-17 2000-03-28 Furukawa Electric Co Ltd:The Base sheet for electronic apparatus made of aluminum base composite material and its production
JP2005068445A (en) * 2003-08-25 2005-03-17 Dowa Mining Co Ltd Metallic member covered with metal
WO2010005088A1 (en) * 2008-07-11 2010-01-14 第一電子工業株式会社 Electronic component and method for manufacturing the same
JP2010202900A (en) * 2009-03-02 2010-09-16 Alps Electric Co Ltd Method of producing electrical contact
JP2012505964A (en) * 2008-10-17 2012-03-08 アトテック・ドイチュラント・ゲーエムベーハー Ni-P / Pd stack with reduced stress for bondable wafer surfaces
JP2013105629A (en) * 2011-11-14 2013-05-30 Nippon Light Metal Co Ltd Current collector plate for fuel cell and method for manufacturing the same
JP2013204102A (en) * 2012-03-29 2013-10-07 Yamaichi Electronics Co Ltd Method for producing electric contact

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000087291A (en) * 1998-09-17 2000-03-28 Furukawa Electric Co Ltd:The Base sheet for electronic apparatus made of aluminum base composite material and its production
JP2005068445A (en) * 2003-08-25 2005-03-17 Dowa Mining Co Ltd Metallic member covered with metal
WO2010005088A1 (en) * 2008-07-11 2010-01-14 第一電子工業株式会社 Electronic component and method for manufacturing the same
JP2012505964A (en) * 2008-10-17 2012-03-08 アトテック・ドイチュラント・ゲーエムベーハー Ni-P / Pd stack with reduced stress for bondable wafer surfaces
JP2010202900A (en) * 2009-03-02 2010-09-16 Alps Electric Co Ltd Method of producing electrical contact
JP2013105629A (en) * 2011-11-14 2013-05-30 Nippon Light Metal Co Ltd Current collector plate for fuel cell and method for manufacturing the same
JP2013204102A (en) * 2012-03-29 2013-10-07 Yamaichi Electronics Co Ltd Method for producing electric contact

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