WO2023189418A1 - 電気接点材料、ならびにこれを用いた接点、端子およびコネクタ - Google Patents

電気接点材料、ならびにこれを用いた接点、端子およびコネクタ Download PDF

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Publication number
WO2023189418A1
WO2023189418A1 PCT/JP2023/009299 JP2023009299W WO2023189418A1 WO 2023189418 A1 WO2023189418 A1 WO 2023189418A1 JP 2023009299 W JP2023009299 W JP 2023009299W WO 2023189418 A1 WO2023189418 A1 WO 2023189418A1
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Prior art keywords
silver
containing layer
electrical contact
layer
less
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PCT/JP2023/009299
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English (en)
French (fr)
Japanese (ja)
Inventor
義胤 鳥居
秀一 北河
颯己 葛原
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Furukawa Electric Co Ltd
Furukawa Automotive Systems Inc
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Furukawa Electric Co Ltd
Furukawa Automotive Systems Inc
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Application filed by Furukawa Electric Co Ltd, Furukawa Automotive Systems Inc filed Critical Furukawa Electric Co Ltd
Priority to US18/579,877 priority Critical patent/US12542222B2/en
Priority to JP2023537268A priority patent/JPWO2023189418A1/ja
Priority to CN202380011159.0A priority patent/CN117222782A/zh
Priority to EP23779442.5A priority patent/EP4502246A4/en
Publication of WO2023189418A1 publication Critical patent/WO2023189418A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • 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
    • C22C5/06—Alloys based on silver
    • 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
    • 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
    • C23C28/021—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 including at least one metal alloy layer
    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
    • H01R13/02—Contact members
    • H01R13/03—Contact members characterised by the material, e.g. plating, or coating materials

Definitions

  • the present disclosure relates to electrical contact materials, and contacts, terminals, and connectors using the same.
  • Patent Document 1 discloses that the surface of a base material made of copper or copper alloy is coated with a silver plating layer, and the silver plating layer is separated from the first silver plating layer on the lower layer side and the first silver plating layer.
  • a silver-plated terminal for a connector is described, which is composed of a second silver-plated layer above a silver-plated layer, and in which the crystal grain size of the first silver-plated layer is larger than the crystal grain size of the second silver-plated layer.
  • Patent Document 1 discloses that, regarding silver-plated materials, the crystal grain size of the silver-plated layer tends to increase due to recrystallization, and this increase in crystal grain size lowers hardness and reduces wear resistance.
  • the crystal grain size of the silver plating layer is specified as a material with good wear resistance. However, the size of the crystal grains depends on the thickness of the plating layer. Therefore, in order to obtain good wear resistance in Patent Document 1, there is a restriction on the thickness of the silver plating layer.
  • Patent Document 2 in a silver plating solution containing silver, potassium cyanide, and selenium at a predetermined concentration, y and x are A method for producing a silver-plated material in which a silver plating film with a purity of 99.9% by mass or more is formed on a base material by electroplating so that a predetermined relationship is achieved.
  • Patent Document 2 exemplifies a method for manufacturing a silver-plated material that suppresses an increase in contact resistance while maintaining high hardness by containing elements such as selenium in the silver-plated film, and Vickers hardness is the basis for wear resistance. In this manner, in Patent Document 2, the Vickers hardness of the silver-plated material, which depends on the characteristics of the base material, is used to evaluate the wear resistance. However, it is originally necessary to evaluate the wear resistance of the plating film itself, which is not easily affected by the characteristics of the base material.
  • An object of the present disclosure is to provide an electrical contact material with excellent wear resistance that is not easily affected by base material properties, and contacts, terminals, and connectors using the same.
  • An electrical contact material comprising an electrically conductive base material and a silver-containing layer containing silver provided on at least a part of the surface of the electrically conductive base material, wherein the silver-containing layer is provided in a cross section of the electrical contact material.
  • An electrical contact material wherein the average GOS value of the layer is 1.00° or less, and the proportion of KAM values of 1.00° or more is 20% or more.
  • the silver-containing layer has an average crystal grain size of 0.2 ⁇ m or more and 2.0 ⁇ m or less.
  • an electrical contact material having excellent wear resistance that is not easily affected by base material properties, and contacts, terminals, and connectors using the same.
  • FIG. 1 is a cross-sectional view showing an example of an electrical contact material according to an embodiment.
  • FIG. 2 is a sectional view showing another example of the electrical contact material of the embodiment.
  • the present inventors have focused on the amount of strain in the silver-containing layer provided on at least a portion of the surface of the conductive base material, and have found that it is possible to control the GOS value and KAM value of the silver-containing layer. discovered that the wear resistance of electrical contact materials is excellent regardless of the characteristics of the conductive base material, and based on this knowledge, the present disclosure was completed.
  • the electrical contact material of the embodiment includes an electrically conductive base material and a silver-containing layer containing silver provided on at least a portion of the surface of the electrically conductive base material, and in a cross section of the electrical contact material, the silver-containing layer
  • the average GOS value is 1.00° or less, and the proportion of KAM values of 1.00° or more is 20% or more.
  • FIG. 1 is a cross-sectional view showing an example of an electrical contact material according to an embodiment.
  • the electrical contact material 1 includes a conductive base material 10 and a silver-containing layer 20.
  • the conductive base material 10 constituting the electrical contact material 1 is a rolled material that has conductivity and is obtained by rolling.
  • the conductive base material 10 is made of a copper-based material containing pure copper and a copper alloy, or an iron-based material containing pure iron and an iron alloy.
  • it is made of a material.
  • Cu-Zn based, Cu-Ni-Si based, Cu-Sn-Ni based, Cu-Cr-Mg based, and Cu-Ni-Si-Zn-Sn-Mg based copper alloys are preferred. .
  • the electrical conductivity of the conductive base material 10 is preferably 60% IACS or more, more preferably 80% IACS or more. When the electrical conductivity of the conductive base material 10 is 60% IACS or more, the electrical contact material 1 has good electrical conductivity.
  • the shape of the conductive base material 10 may be appropriately selected depending on the use of the electrical contact material 1, but it is preferably strip-shaped, plate-shaped, rod-shaped, or linear.
  • the silver-containing layer 20 constituting the electrical contact material 1 is provided on at least a portion of the surface of the conductive base material 10 and contains silver.
  • the silver-containing layer 20 covering the surface of the conductive substrate 10 is made of pure silver or a silver alloy, preferably pure silver, that is, the silver-containing layer 20 is preferably a pure silver layer. From the viewpoint that the electrical contact material 1 has excellent abrasion resistance and the abrasion resistance of the electrical contact material 1 is not easily influenced by the characteristics of the conductive base material 10, the silver-containing layer 20 is formed by plating, i.e. It is preferable that the silver-containing layer 20 is a plating film.
  • the average GOS value of the silver-containing layer 20 is 1.00° or less, and the proportion of KAM values of 1.00° or more is 20% or more.
  • the cross section of the electrical contact material 1 is a cross section parallel to the rolling direction of the conductive base material 10.
  • the average GOS value of the silver-containing layer 20 in the cross section of the electrical contact material 1 is 1.00° or less, the amount of strain remaining in the crystal grains in the silver-containing layer 20 is low, and the KAM of 1.00° or more When the value ratio is 20% or more, the amount of strain remaining in the silver-containing layer 20 can be maintained high, and the hardness increases, so that wear resistance can be improved.
  • the average GOS value of the silver-containing layer 20 in the cross section of the electrical contact material 1 is 1.00° or less, preferably 0.75° or less, and more preferably 0.50° or less. Further, in the cross section of the electrical contact material 1, the ratio of the KAM value of the silver-containing layer 20 at 1.00° or more is 20% or more, and more preferably 25% or more.
  • the ratio of KAM values of 1.00° or more is preferably 50% or less.
  • the ratio of KAM values of 1.00° or more in the silver-containing layer 20 is 50% or less, deterioration in bending workability due to an excessive amount of strain in the silver-containing layer 20 can be suppressed.
  • the GOS (Grain Orientation Spread) value is the average value of the orientation difference between a certain measurement point i and all measurement points (including measurement point i) within a crystal grain, and is a change in the overall crystal orientation of the crystal grain. It is a parameter that reflects the local orientation difference, and is the value obtained by integrating the local orientation difference. While the KAM value is a value that reflects the local amount of strain within the silver-containing layer 20, the GOS value is a value that reflects the average amount of strain within the silver-containing layer 20.
  • the GOS value can be expressed by the following equation (1).
  • ⁇ ij Crystal orientation difference between measurement point i and measurement point j
  • n g Number of measurement points in crystal grain
  • the GOS value is a parameter that reflects changes in the overall crystal orientation of crystal grains, and corresponds to the integral of the local orientation difference (KAM value). Further, the GOS value depends on the crystal grain size, and is considered to increase as the crystal grain becomes larger.
  • the KAM (Kernel Average Misorientation) value at the measurement point i is the average value of the orientation difference between a certain measurement point i and the measurement point j adjacent to the measurement point i, and is a value that reflects the amount of strain in the silver-containing layer 20. be.
  • the KAM value can be expressed by the following equation (2).
  • ⁇ ij Crystal orientation difference between measurement point i and measurement point j
  • n Number of measurement points j adjacent to measurement point i
  • the KAM value is calculated for all measurement points within the field of view, and their average value is taken as the representative value for that field of view, and tends to increase at locations with large strain and near grain boundaries.
  • the GOS value and KAM value are crystals measured continuously using an EBSD detector (manufactured by TSL Solutions, OIM5.0 HIKARI) attached to a high-resolution scanning analytical electron microscope (manufactured by JEOL Ltd., JSM-7001FA). It can be obtained from crystal orientation analysis data calculated from orientation data using analysis software (OIM Analysis, manufactured by TSL Solutions).
  • the object to be measured is the surface of the silver-containing layer 20 on the cross section of the electrical contact material 1 parallel to the rolling direction of the conductive base material 10, which has been mirror-finished using a cross-section polisher (manufactured by JEOL Ltd.), and the measurement magnification is 30,000. It's double.
  • Measurement is performed in steps with a measurement interval of 50 nm or less, excluding measurement points whose CI value analyzed by analysis software is 0.1 or less (noise removal), and where the orientation difference between adjacent pixels is 5.00° or more.
  • the boundary is regarded as a grain boundary, and the GOS value and KAM value are obtained.
  • the average GOS value and the average KAM value can be obtained by performing this measurement multiple times (in multiple different measurement regions of the same sample) and calculating the average value. Further, from the KAM value, the ratio of KAM values of 1.00° or more can be obtained.
  • the average GOS value and the average KAM value are the average value of the GOS value and the average value of the KAM value in the measurement area of the silver-containing layer measured at a magnification of 30,000 times, and the percentage of the KAM value of 1.00° or more is the ratio of the KAM value of 1.00° or more to the KAM value of the measurement area of the silver-containing layer measured at a magnification of 30,000 times.
  • the average crystal grain size in the silver-containing layer 20 is preferably 0.2 ⁇ m or more, more preferably 0.4 ⁇ m or more, and even more preferably 0.6 ⁇ m or more.
  • wear resistance can be further improved.
  • the average crystal grain size in the silver-containing layer 20 is preferably 2.0 ⁇ m or less, more preferably 1.5 ⁇ m or less, and still more preferably 1.0 ⁇ m or less. When the average crystal grain size in the silver-containing layer 20 is 2.0 ⁇ m or less, wear resistance can be stably maintained.
  • the silver-containing layer 20 may include one or more elements (hereinafter also referred to as a second element) selected from the group consisting of Sn, Zn, In, Ni, Cu, Se, Sb, and Co.
  • a second element selected from the group consisting of Sn, Zn, In, Ni, Cu, Se, Sb, and Co.
  • the silver-containing layer 20 is made of one or more types selected from the group consisting of Sn, Zn, In, Ni, Cu, Se, Sb, and Co.
  • the total content of the elements is less than 15.0 at%.
  • the silver-containing layer 20 is selected from the group consisting of Sn, Zn, In, Ni, Cu, Se, Sb, and Co. It is preferable that the total content of one or more elements is 0.1 at% or more.
  • the lower limit of the average thickness of the silver-containing layer 20 is preferably 0.5 ⁇ m or more, more preferably 2.0 ⁇ m or more, and still more preferably 3.0 ⁇ m or more.
  • the upper limit of the average thickness of the silver-containing layer 20 is preferably 5.0 ⁇ m or less.
  • the lower limit of the average thickness of the silver-containing layer 20 is 0.5 ⁇ m or more, the excellent wear resistance of the electrical contact material 1 can be maintained for a long period of time.
  • the upper limit of the average thickness of the silver-containing layer 20 is 5.0 ⁇ m or less, material costs can be suppressed.
  • FIG. 2 is a sectional view showing another example of the electrical contact material of the embodiment.
  • the electrical contact material 2 shown in FIG. 2 has basically the same structure as the electrical contact material 1 shown in FIG. 1 except that the structure of the intermediate layer 30 is added.
  • the electrical contact material 2 further includes an intermediate layer 30 made of nickel or a nickel alloy between the conductive base material 10 and the silver-containing layer 20.
  • an intermediate layer 30 made of nickel or a nickel alloy between the conductive base material 10 and the silver-containing layer 20.
  • the intermediate layer 30 is provided between the surface of the conductive base material 10 and the silver-containing layer 20, thermal diffusion of elements constituting the conductive base material 10 into the silver-containing layer 20 is suppressed, and the conductive base material The adhesion between the silver-containing layer 10 and the silver-containing layer 20 can be improved.
  • the intermediate layer 30 is preferably made of pure nickel or a Ni-P-based nickel alloy.
  • the lower limit of the average thickness of the intermediate layer 30 is preferably 0.01 ⁇ m or more, more preferably 0.10 ⁇ m or more, and still more preferably 0.30 ⁇ m or more.
  • the upper limit of the average thickness of the intermediate layer 30 is preferably 3.00 ⁇ m or less, more preferably 2.00 ⁇ m or less, and still more preferably 1.00 ⁇ m or less. If the lower limit of the average thickness of the intermediate layer 30 is less than 0.01 ⁇ m, the above-mentioned suppression of thermal diffusion and improvement of adhesion cannot be achieved. If the upper limit of the average thickness of the intermediate layer 30 is more than 3.00 ⁇ m, bending workability deteriorates. When an electrical contact material is used in a terminal, bending workability of R/t ⁇ 1 is required.
  • the electrical contact materials 1 and 2 described above may further include a copper layer (not shown) directly below the silver-containing layer 20, which is the surface layer.
  • the copper layer (not shown) is made of pure copper or a copper alloy.
  • the thickness of the copper layer (not shown) is significantly smaller than the thickness of the conductive base material 10.
  • the electrical contact materials 1 and 2 have excellent abrasion resistance that is not easily affected by the characteristics of the conductive base material 10, so the electrical contact materials 1 and 2 are suitable for contacts, terminals, and connectors. Can be used. These contacts are contacts made using electrical contact materials 1 and 2, terminals are terminals made using electrical contact materials 1 and 2, and connectors are made using electrical contact materials 1 and 2. This is a connector made using
  • a silver-containing layer is formed on at least a portion of the surface of a conductive base material by a plating method or the like. Subsequently, the base material provided with the silver-containing layer on the surface is rolled. In this way, the electrical contact material 1 can be manufactured.
  • an intermediate layer is formed on at least a portion of the surface of the conductive base material by a plating method or the like.
  • a silver-containing layer is formed on the intermediate layer by a plating method or the like.
  • the substrate comprising the intermediate layer and the silver-containing layer is rolled. In this way, the electrical contact material 2 can be manufactured.
  • the plating conditions for the silver-containing layer by setting the current density to 5 A/dm 2 or more and 10 A/dm 2 or less and the bath temperature (liquid temperature) to 25°C or more to prioritize nucleation, crystal grains with different crystal orientations can be formed. Since the silver-containing layer grows in large numbers and the difference in crystal orientation increases, the internal stress of the silver-containing layer can be further increased.
  • the KAM value in the silver-containing layer can be controlled to control the proportion of KAM values of 1.00° or more in the silver-containing layer to 20% or more.
  • the proportion of KAM values of 1.00° or more is less than 20%. Furthermore, even if the temperature is 25°C or higher, if the current density exceeds 10A/ dm2 , the proportion of KAM values of 1.00° or higher will be less than 20% due to excessive fine crystals. The surface hardness is too high, resulting in poor bending workability.
  • the processing rate of the rolling process is 5% or more and 15% or less.
  • the processing rate of rolling is a percentage obtained by dividing the difference between the cross-sectional area of the sample before rolling and the cross-sectional area of the sample after rolling by the cross-sectional area of the sample before rolling.
  • the rolling ratio is less than 5% or no rolling is performed, the amount of strain at grain boundaries will be small, and the number of measurement points with KAM values of 1.00° or more will decrease, resulting in KAM values of 1.00° or more in the silver-containing layer. As the ratio of values becomes smaller, the ratio of KAM values of 1.00° or more becomes less than 20%.
  • heat treatment is performed at 300° C. or higher and 600° C. or lower for 5 seconds or more and 60 seconds or less.
  • the strain introduced by plating can be made uniform.
  • the strain within the crystal grains is released, thereby making it possible to control the average GOS value of the silver-containing layer to 1.00° or less.
  • the strain within the silver-containing layer is present mostly at the grain boundaries, and measurement points showing KAM values of 1.00° or more are located near the grain boundaries. Since it can be aggregated, the ratio of KAM values of 1.00° or more can be controlled to 20% or more.
  • heat treatment if the heat treatment temperature is less than 300°C or the heat treatment time is less than 5 seconds, the strain within the grains cannot be sufficiently released, and the measurement points showing a KAM value of 1.00° or more are separated from the grain boundaries. Since they cannot be aggregated in the vicinity, it is not possible to achieve a ratio of KAM values with an average GOS value of 1.00° or less and 1.00° or more of 20% or more.
  • heat treatment even if the heat treatment temperature is over 600°C or the heat treatment time is over 60 seconds, the percentage of KAM values with an average GOS value of 1.00° or less and 1.00° or more is 20% or more. Furthermore, excessive heat treatment reduces material strength, making it impossible to maintain sufficient strength when used in contacts, terminals, and connectors.
  • the second element is A silver-containing layer containing elements may be directly formed.
  • a silver-containing layer containing a second element may be formed by alternately forming a silver-containing layer and a second element layer by plating or the like, and then performing heat treatment. good.
  • the processing rate of the rolling process is preferably 5% or more and 15% or less from the same viewpoint as above.
  • the heat treatment in this case may be replaced by a heat treatment performed after forming the above-described silver-containing layer and before rolling.
  • the influence of the base material properties can be reduced. It is possible to obtain an electrical contact material that has excellent wear resistance and is not susceptible to wear.
  • Examples 1 to 5 The base material (manufactured by Furukawa Electric, EFTEC-550T, 80% IACS) was electrolytically degreased and then acid washed. Thereafter, a silver-containing layer was formed on the substrate surface by plating (current density 10 A/dm 2 ) in an alkali cyanide silver bath (silver cyanide 50 g/L, potassium cyanide 100 g/L) at a bath temperature of 25°C, and then Heat treatment was performed at 300° C. or higher and 600° C. or lower for 5 seconds or more and 60 seconds or less. Subsequently, electrical contact materials having the silver-containing layer (pure silver layer) shown in Table 1 were manufactured by rolling at the processing rate shown in Table 1.
  • Example 6 to 14 The base material (manufactured by Furukawa Electric, EFTEC-550T, 80% IACS) was electrolytically degreased and then acid washed. Thereafter, a silver-containing layer was formed on the substrate surface by plating (current density 10 A/dm 2 ) in an alkali cyanide silver bath (silver cyanide 50 g/L, potassium cyanide 100 g/L) at a bath temperature of 25°C, and then A tin layer is formed by plating method (current density 10 A/dm 2 ) in a sulfuric acid bath (tin sulfate 80 g/L, sulfuric acid 80 g/L) at a bath temperature of 25°C, and then heated at 300°C or higher and 600°C or lower for 5 seconds or more. Heat treatment was performed for 60 seconds or less. Subsequently, electrical contact materials having the silver-containing layer (silver alloy layer) shown in Table 1 were manufactured by rolling at the processing rate shown in Table
  • Example 15 to 19 The base material (manufactured by Furukawa Electric, EFTEC-550T, 80% IACS) was electrolytically degreased and then acid washed. Thereafter, the intermediate layer was plated using a plating method (current density 15 A/dm 2 ) in a nickel plating bath (nickel sulfate hexahydrate 500 g/L, nickel chloride 30 g/L, boric acid 30 g/L) at a bath temperature of 55°C.
  • a plating method current density 15 A/dm 2
  • a nickel plating bath nickel sulfate hexahydrate 500 g/L, nickel chloride 30 g/L, boric acid 30 g/L
  • a silver-containing layer is then formed on the surface of the intermediate layer by plating (current density 10 A/dm 2 ) in an alkali cyanide silver bath (silver cyanide 50 g/L, potassium cyanide 100 g/L) at a bath temperature of 25°C. Then, heat treatment was performed at 300° C. or higher and 600° C. or lower for 5 seconds or more and 60 seconds or less. Subsequently, rolling was performed at the processing rates shown in Table 1 to produce electrical contact materials including the silver-containing layer (pure silver layer) and intermediate layer (pure nickel layer) shown in Table 1.
  • a silver-containing layer is then formed on the surface of the intermediate layer by plating (current density 10 A/dm 2 ) in an alkali cyanide silver bath (silver cyanide 50 g/L, potassium cyanide 100 g/L) at a bath temperature of 25°C. was formed, followed by a heat treatment at a temperature below 300°C or above 600°C for less than 5 seconds. Subsequently, rolling was performed at the processing rates shown in Table 1 to produce electrical contact materials including the silver-containing layer (pure silver layer) and intermediate layer (pure nickel layer) shown in Table 1. Note that in Comparative Example 3, rolling was not performed.
  • Example 20 to 34 The base material (manufactured by Furukawa Electric, EFTEC-550T, 80% IACS) was electrolytically degreased and then acid washed. Thereafter, the intermediate layer was plated using a plating method (current density 15 A/dm 2 ) in a nickel plating bath (nickel sulfate hexahydrate 500 g/L, nickel chloride 30 g/L, boric acid 30 g/L) at a bath temperature of 55°C.
  • a plating method current density 15 A/dm 2
  • a nickel plating bath nickel sulfate hexahydrate 500 g/L, nickel chloride 30 g/L, boric acid 30 g/L
  • a silver-containing layer is formed on the material surface using a plating method (current density 5-10 A/d) in an alkali cyanide silver bath (silver cyanide 50-100 g/L, potassium cyanide 100-200 g/L) at a bath temperature of 25°C. 2 ) is formed on the surface of the intermediate layer, and then a tin layer is formed by plating method (current density 10 to 20 A/dm 2 ) in a sulfuric acid bath (tin sulfate 80 g/L, sulfuric acid 80 g/L) at a bath temperature of 25°C. Then, heat treatment was performed at 300° C. or more and 600° C. or less for 5 seconds or more and 60 seconds or less. Subsequently, rolling was performed at the processing rates shown in Table 1 to produce electrical contact materials having the silver-containing layer (silver alloy layer) and intermediate layer (pure nickel layer) shown in Table 1.
  • a plating method current density 5-10 A/d
  • a silver-containing layer is formed on the material surface using a plating method (current density 5-10 A/d) in an alkali cyanide silver bath (silver cyanide 50-100 g/L, potassium cyanide 100-200 g/L) at a bath temperature of 25°C. 2 ) is formed on the surface of the intermediate layer, and then a tin layer is formed by plating method (current density 10 to 20 A/dm 2 ) in a sulfuric acid bath (tin sulfate 80 g/L, sulfuric acid 80 g/L) at a bath temperature of 25°C. Then, a heat treatment was performed at a temperature lower than 300°C or higher than 600°C for less than 5 seconds. Subsequently, rolling was performed at the processing rates shown in Table 1 to produce electrical contact materials having the silver-containing layer (silver alloy layer) and intermediate layer (pure nickel layer) shown in Table 1. Note that in Comparative Example 8, no intermediate layer was formed.
  • Examples 35 to 37 The base material (manufactured by Furukawa Electric, EFTEC-550T, 80% IACS) was electrolytically degreased and then acid washed. After that, an intermediate layer was formed in a nickel-phosphorous electrolytic bath (nickel sulfate hexahydrate 500 g/L, nickel chloride hexahydrate 30 g/L, boric acid 30 g/L, phosphorous acid 16 g/L) at a bath temperature of 55°C.
  • a nickel-phosphorous electrolytic bath nickel sulfate hexahydrate 500 g/L, nickel chloride hexahydrate 30 g/L, boric acid 30 g/L, phosphorous acid 16 g/L
  • Example 38-55 The base material (manufactured by Furukawa Electric, EFTEC-550T, 80% IACS) was electrolytically degreased and then acid washed. Thereafter, the intermediate layer was plated using a plating method (current density 15 A/dm 2 ) in a nickel plating bath (nickel sulfate hexahydrate 500 g/L, nickel chloride 30 g/L, boric acid 30 g/L) at a bath temperature of 55°C.
  • a plating method current density 15 A/dm 2
  • a nickel plating bath nickel sulfate hexahydrate 500 g/L, nickel chloride 30 g/L, boric acid 30 g/L
  • the surface of the silver-containing layer on the mirror-finished surface of the cross section of the electrical contact material parallel to the rolling direction of the conductive base material was obtained as the measurement target.
  • the measurement magnification was 30,000 times. Measurement is performed in steps with a measurement interval of 50 nm or less, excluding measurement points with a CI value of 0.1 or less analyzed by analysis software, and boundaries where the orientation difference between adjacent pixels is 5.00° or more are defined as crystal grains.
  • GOS and KAM values were obtained. This measurement was performed five times (in five different measurement areas of the same sample), and the average value was calculated to obtain the average GOS value and average KAM value of the silver-containing layer. Further, from the KAM value, the proportion of the KAM value of 1.00° or more in the silver-containing layer was calculated.
  • Average crystal grain size A cross-section of the electrical contact material parallel to the rolling direction of the conductive base material was mirror-finished using a cross-section polisher (manufactured by JEOL), and the surface of the silver-containing layer was observed at a magnification of 30,000. In the SEM image obtained as a magnification, the average crystal grain size in the silver-containing layer was obtained by a cutting method using a line segment perpendicular to the plating thickness direction.
  • Coefficient of kinetic friction is less than 0.4 ⁇ : Coefficient of kinetic friction is 0.4 or more and less than 0.6 ⁇ : Coefficient of kinetic friction is 0.6 or more
  • ⁇ The ratio of the depth from the reference plane to the thickness of the silver-containing layer is less than 1/10.
  • ⁇ The ratio of the depth from the reference plane to the thickness of the silver-containing layer is 1/10 or more and less than 1/5.
  • ⁇ The ratio of the depth from the reference plane to the thickness of the silver-containing layer is 1/5 or more
  • ⁇ Contact resistance value is less than 0.3 m ⁇ ⁇ : Contact resistance value is 0.3 m ⁇ or more and less than 0.8 m ⁇ ⁇ : Contact resistance value is 0.8 m ⁇ or more
  • ⁇ Contact resistance value after heating is less than 1.0 m ⁇ ⁇ : Contact resistance value after heating is 1.0 m ⁇ or more and less than 5.0 m ⁇ ⁇ : Contact resistance value after heating is 5.0 m ⁇ or more
  • the average GOS value in the silver-containing layer was 1.00° or less, and the proportion of KAM values of 1.00° or more was 20% or more. Therefore, the wear resistance of the electrical contact material was not affected by the characteristics of the conductive base material and was good.
  • the average GOS value in the silver-containing layer was 1.00° or less, and the proportion of KAM values of 1.00° or more was outside the range of 20% or more, so the electrical contact The wear resistance of the material was poor.

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PCT/JP2023/009299 2022-03-30 2023-03-10 電気接点材料、ならびにこれを用いた接点、端子およびコネクタ Ceased WO2023189418A1 (ja)

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US18/579,877 US12542222B2 (en) 2022-03-30 2023-03-10 Electrical contact material, and contact, terminal and connector made using this
JP2023537268A JPWO2023189418A1 (https=) 2022-03-30 2023-03-10
CN202380011159.0A CN117222782A (zh) 2022-03-30 2023-03-10 电接点材料以及使用其的接点、端子及连接器
EP23779442.5A EP4502246A4 (en) 2022-03-30 2023-03-10 ELECTRICAL CONTACT MATERIAL, AND TERMINAL, CONNECTOR AND CONTACT USING IT

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EP4502247A4 (en) * 2022-03-30 2026-01-14 Furukawa Electric Co Ltd ELECTRICAL CONTACT MATERIAL, AND CONTACT, TERMINAL AND CONNECTOR USING IT

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JPH052940A (ja) * 1991-06-25 1993-01-08 Furukawa Electric Co Ltd:The 電気接点材料とその製造方法
JP2008169408A (ja) 2007-01-09 2008-07-24 Auto Network Gijutsu Kenkyusho:Kk コネクタ用銀めっき端子
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JP6611602B2 (ja) 2015-01-30 2019-11-27 Ｄｏｗａメタルテック株式会社 銀めっき材およびその製造方法
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JP2020041210A (ja) * 2018-09-07 2020-03-19 信越理研シルコート工場株式会社 高耐久性銀めっきフープ材
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FR2639466B1 (fr) * 1988-11-22 1991-02-15 Telemecanique Procede de preparation d'un materiau de contact electrique et procede de fabrication d'un element de contact incorporant un tel materiau
JP5387742B2 (ja) * 2012-04-06 2014-01-15 株式会社オートネットワーク技術研究所 めっき部材、コネクタ用めっき端子、めっき部材の製造方法、及びコネクタ用めっき端子の製造方法
JP6079508B2 (ja) * 2013-08-29 2017-02-15 株式会社オートネットワーク技術研究所 めっき部材、コネクタ用めっき端子、めっき部材の製造方法、およびコネクタ用めっき端子の製造方法
JP6601276B2 (ja) * 2016-03-08 2019-11-06 株式会社オートネットワーク技術研究所 電気接点およびコネクタ端子対

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JPS524436A (en) * 1975-06-30 1977-01-13 Nagayasu Kichisuke Method of producing metal material for plating
JPS6372895A (ja) * 1986-09-17 1988-04-02 Nippon Mining Co Ltd 電子・電気機器用部品の製造方法
JPH052940A (ja) * 1991-06-25 1993-01-08 Furukawa Electric Co Ltd:The 電気接点材料とその製造方法
JP2008169408A (ja) 2007-01-09 2008-07-24 Auto Network Gijutsu Kenkyusho:Kk コネクタ用銀めっき端子
JP2015030892A (ja) * 2013-08-05 2015-02-16 株式会社Ｓｈカッパープロダクツ 銅条、めっき付銅条及びリードフレーム
JP6611602B2 (ja) 2015-01-30 2019-11-27 Ｄｏｗａメタルテック株式会社 銀めっき材およびその製造方法
JP2020026566A (ja) * 2018-08-17 2020-02-20 信越理研シルコート工場株式会社 圧延材
JP2020041210A (ja) * 2018-09-07 2020-03-19 信越理研シルコート工場株式会社 高耐久性銀めっきフープ材
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JPWO2023189418A1 (https=) 2023-10-05
EP4502246A1 (en) 2025-02-05

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