WO2022137613A1 - Agめっき材、Agめっき材の製造方法、および、電気部品 - Google Patents
Agめっき材、Agめっき材の製造方法、および、電気部品 Download PDFInfo
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- WO2022137613A1 WO2022137613A1 PCT/JP2021/026414 JP2021026414W WO2022137613A1 WO 2022137613 A1 WO2022137613 A1 WO 2022137613A1 JP 2021026414 W JP2021026414 W JP 2021026414W WO 2022137613 A1 WO2022137613 A1 WO 2022137613A1
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- 239000000463 material Substances 0.000 title claims abstract description 225
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 238000007747 plating Methods 0.000 claims abstract description 480
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 65
- 239000011148 porous material Substances 0.000 claims description 42
- 239000000758 substrate Substances 0.000 claims description 28
- 239000010410 layer Substances 0.000 description 255
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 147
- 230000000052 comparative effect Effects 0.000 description 24
- 238000009713 electroplating Methods 0.000 description 24
- 229910052802 copper Inorganic materials 0.000 description 23
- 239000010949 copper Substances 0.000 description 23
- 229910052759 nickel Inorganic materials 0.000 description 23
- 239000000243 solution Substances 0.000 description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 19
- 229910052709 silver Inorganic materials 0.000 description 18
- 239000000523 sample Substances 0.000 description 17
- 238000000177 wavelength dispersive X-ray spectroscopy Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 239000004332 silver Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 2
- TXRHHNYLWVQULI-UHFFFAOYSA-L nickel(2+);disulfamate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O TXRHHNYLWVQULI-UHFFFAOYSA-L 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 2
- 229940098221 silver cyanide Drugs 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000150258 Prospect Hill orthohantavirus Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- -1 nickel organic acid Chemical class 0.000 description 1
- VSRIZRHGMXKDIK-UHFFFAOYSA-N nickel sulfamic acid tetrahydrate Chemical compound O.O.O.O.[Ni].S(N)(O)(=O)=O VSRIZRHGMXKDIK-UHFFFAOYSA-N 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000218 poly(hydroxyvalerate) Polymers 0.000 description 1
- HKSGQTYSSZOJOA-UHFFFAOYSA-N potassium argentocyanide Chemical compound [K+].[Ag+].N#[C-].N#[C-] HKSGQTYSSZOJOA-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
-
- 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
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/623—Porosity of the layers
-
- 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
- H01R43/00—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors
- H01R43/16—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors for manufacturing contact members, e.g. by punching and by bending
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/46—Electroplating: Baths therefor from solutions of silver
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H1/00—Contacts
- H01H1/02—Contacts characterised by the material thereof
- H01H1/021—Composite material
-
- 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 invention relates to an Ag plating material, a method for manufacturing an Ag plating material, and an electric component.
- the conductor material is silver-plated to prevent oxidation of the conductor material such as copper and copper alloy due to heating during the sliding process.
- a silver (Ag) plating material is used.
- Patent Document 1 describes a plated product in which a multilayer plating film is formed on a base material made of a conductive metal, and a porous plating layer containing Ni or Cu as a main component and Au Alternatively, a plated product is described in which a surface plating layer containing Ag as a main component is provided in this order, and a large number of holes are formed on the surface of the multilayer plating film (claim 1).
- Patent Document 1 discloses the following contents as a reason for forming a large number of holes on the surface of the multilayer plating film ([0020]).
- the surface plating layer is formed along the unevenness of the porous plating layer, and holes are also formed in the surface plating layer.
- the surface plating layer is likely to be formed on the convex portion of the surface of the porous plating layer, and the surface plating layer is difficult to be formed on the bottom surface and the side surface of the pores formed on the surface of the porous plating layer. As a result, there will be a portion where the surface plating layer is not formed and a portion where the thickness of the surface plating layer is thin.
- the non-uniformity of the surface plating layer containing Au or Ag as a main component can prevent the concentration of corrosion currents that cause galvanic corrosion, and rather improve the corrosion resistance.
- Patent Document 2 describes that the surface of the plating film described in Patent Document 1 has a large number of pores, and the pores are filled with lubricating particles by a blast treatment to provide slidability (Patent Document 2). wrap up).
- a base material made of a metal material and a base material provided on the base material are provided in order to have excellent wear resistance and to maintain good electrical connectivity for a long period of time even if the connector is repeatedly inserted and removed. It has a porous metal layer having a large number of pores and a filling portion filled in the pores in the porous metal layer, and the filling portion is a metal material constituting the porous metal layer.
- An electrical contact material for a connector made of a metal material having a lower hardness than that of the other is described (summary, claim 1).
- a surface layer made of silver is formed on the surface of a base layer made of nickel formed on a base material to provide a silver plating material having excellent wear resistance, and the silver plating material is provided.
- the surface of the base material is roughened, and after forming a base layer made of nickel on the surface of the roughened base material, or after forming a base layer made of nickel on the base material, a base layer made of nickel is formed. It is described that after the surface of the underlayer is roughened, a surface layer made of silver is formed on the surface of the underlayer (both are summarized, claim 1).
- a silver-plated copper material is often used for electric vehicles from the viewpoint of electrical conductivity and contact reliability.
- the characteristics required for such a high-voltage terminal are insertion / removal resistance and wear resistance (collectively referred to as wear resistance in the present specification), and are preferably capable of withstanding fine sliding wear (resistance to slight sliding wear). Vibration).
- An object of the present invention is to provide an Ag plating material having excellent wear resistance.
- the first aspect of the present invention is An Ag plating material in which an Ag plating layer is formed on a base material made of a conductive metal.
- a two-layer plating structure having a porous Ni plating layer and an Ag plating layer in this order is formed on the base material from the base material side, and the Ag plating material having a plurality of these two-layer plating structures is provided. Is.
- the second aspect of the present invention is the aspect described in the first aspect.
- a base Ni plating layer is further formed between the two-layer plating structure on the most substrate side and the substrate.
- the third aspect of the present invention is the aspect described in the second aspect.
- the thickness of the base Ni plating layer is 0.05 to 2 ⁇ m.
- the fourth aspect of the present invention is the aspect described in any one of the first to third aspects.
- a large number of holes are formed on the surface of the Ag plating material.
- a fifth aspect of the present invention is the aspect described in the fourth aspect.
- the number density of the holes is 5000 to 100,000 / mm 2 .
- the sixth aspect of the present invention is the aspect described in the fourth or fifth aspect.
- the average diameter of the holes is 1 to 10 ⁇ m.
- the seventh aspect of the present invention is the aspect described in any one of the first to sixth aspects.
- the thickness of the porous Ni plating layer is 0.1 to 3 ⁇ m.
- the eighth aspect of the present invention is the aspect described in any one of the first to seventh aspects.
- the thickness of the Ag plating layer is 0.1 to 3 ⁇ m.
- a ninth aspect of the present invention is It is a method for manufacturing an Ag plating material in which an Ag plating layer is formed on a base material made of a conductive metal.
- a two-layer plating structure having a porous Ni plating layer and an Ag plating layer in this order is formed on the base material from the base material side, and a plurality of these two-layer plating structures are formed. It is a manufacturing method.
- the tenth aspect of the present invention is the aspect described in the ninth aspect.
- a base Ni plating layer is further formed between the two-layer plating structure on the most substrate side and the substrate.
- the eleventh aspect of the present invention is the aspect described in the tenth aspect.
- the thickness of the base Ni plating layer is 0.05 to 2 ⁇ m.
- the twelfth aspect of the present invention is the aspect described in any one of the ninth to eleventh aspects.
- the thickness of the porous Ni plating layer is 0.1 to 3 ⁇ m.
- the thirteenth aspect of the present invention is the aspect described in any one of the ninth to twelfth aspects.
- the thickness of the Ag plating layer is 0.1 to 3 ⁇ m.
- the fourteenth aspect of the present invention is It is an electric component which is a contact or terminal component using the Ag plating material according to any one of the first to eighth aspects as a material.
- A is a secondary electron image (2000 times) by EPMA (electron probe microanalyzer) on the surface of the Ag plating material of Example 1.
- B is a reflected electron composition image (2000 times) by EPMA (electron probe microanalyzer) on the surface of the Ag plating material.
- C is a characteristic X-ray image of Ag by WDX (wavelength dispersive X-ray spectroscopy) by EPMA (electron probe microanalyzer) on the surface of the Ag plating material.
- (D) is a characteristic X-ray image of Ni by WDX (wavelength dispersive X-ray spectroscopy) by EPMA (electron probe microanalyzer) on the surface of the Ag plating material.
- (A) is a secondary electron image (2000 times) of the surface of the Ag plating material of Example 1 after the wear resistance test by EPMA (Electron Probe Microanalyzer).
- (B) is a reflected electron composition image (2000 times) by EPMA (electron probe microanalyzer) on the surface of the Ag plating material after the wear resistance test.
- (C) is a characteristic X-ray image of Ag by WDX (wavelength dispersive X-ray spectroscopy) by EPMA (electron probe microanalyzer) on the surface of the Ag plating material after the wear resistance test.
- (D) is a characteristic X-ray image of Ni by WDX (wavelength dispersive X-ray spectroscopy) by EPMA (electron probe microanalyzer) on the surface of the Ag plating material after the wear resistance test. It is a figure explaining the calculation method of the plating film thickness.
- to refers to a predetermined numerical value or more and a predetermined numerical value or less.
- the Ag plating material according to the present embodiment is an Ag plating material in which an Ag plating layer is formed on a base material made of a conductive metal, from the base material side (lower side) on the base material.
- a two-layer plating structure having a porous Ni (nickel) plating layer and an Ag (silver) plating layer in this order is formed, and a plurality of these two-layer plating structures are provided.
- the base material is not limited as long as it is made of a conductive metal, but may be copper or a copper alloy.
- the porous Ni plating layer is a porous plating layer.
- the porous Ni plating layer is a porous Ni plating film having a three-dimensional structure that can be produced by, for example, a known porous Ni plating solution and an electrolytic plating method, and the diameter of the pores when observed from the surface thereof is approximately 1 ⁇ m. It is a hole of several tens of ⁇ m from the front and back, and has a high specific surface area.
- the porous Ni plating layer is a plating layer containing Ni as a main component, and may contain other elements such as P, B, Co, Fe, Cr, Cu, and Zn within the range in which the effect of the present invention is exhibited. ..
- the Ni plating layer and the Ag plating layer mean that Ni and Ag are the main components, respectively.
- the specific Ni content in the porous Ni plating layer is, for example, 90% by mass or more, preferably 95% by mass or more, and further may be 99% by mass or more.
- the thickness of the porous Ni plating layer is preferably 0.1 to 3 ⁇ m. With this thickness, the Ni plating layer can be made porous after appropriately setting the number density of pores and the average diameter of pores.
- the thickness of the porous Ni plating layer is more preferably 0.3 to 2 ⁇ m, and further preferably 0.8 ⁇ m or more.
- the Ag plating layer may be an Ag plating film obtained by performing Ag plating (main plating) after performing Ag strike plating. And it is a plating layer containing Ag as a main component.
- the Ag plating layer may contain other elements such as C, N, S, Se, Sb, Co, Cu, Au, In, P, Zn, Sn, Pd, Bi and the like within the range in which the effect of the present invention is exhibited. ..
- the Ag plating layer formed on the Ag strike plating layer may be referred to as the Ag main plating layer.
- the specific Ag content in the Ag plating layer is, for example, 90% by mass or more, preferably 95% by mass or more, and further may be 99% by mass or more from the viewpoint of conductivity.
- a large number of holes are formed on the surface of the Ag plating material. That is, it is preferable that a large number of holes are observed on the most surface side (exposed surface) of the plurality of Ag plating layers. In addition, a large number of holes may be observed on the upper surface of any of the Ag plating layers constituting the Ag plating material.
- the pores of the Ag plating layer are observed because the surface of the porous Ni plating layer formed under the Ag plating layer is covered with the Ag plating layer, and the Ag plating is not covered until the pores of the porous Ni plating layer are completely filled. It is probable that it was done.
- FIG. 2 is a SIM image (scanning ion microscope image) obtained by observing a cross section of the Ag plating material of the present invention (Example 1) with a SIM (scanning ion microscope). From FIG. 2, it can be confirmed that a two-layer plating structure having a porous Ni plating layer and an Ag plating layer in this order is formed, and a plurality of these two-layer plating structures (three in FIG.
- the two-layer plating structure is provided with three or more layers.
- the porous Ni plating layer is a light gray layer
- the Ag plating layer is a dark gray layer. Unevenness (holes) is observed in the porous Ni plating layer, and Ag plating is formed on the surface thereof.
- the number density of holes on the surface of the Ag plating material and the size of the holes were evaluated.
- shape measurement was performed using an objective lens x 100
- volume / area measurement was performed using a multi-file analysis application
- the analysis range was 100 ⁇ m x 100 ⁇ m.
- the object is at a distance (position) of 0.5 ⁇ m in the depth direction of the Ag plating layer from the reference height.
- the part where (plating surface) is not detected is regarded as a hole (porous part), and the number and area are measured. Then the density of the number of holes per unit area and the average diameter of the holes were calculated. Those having a hole diameter of less than 1 ⁇ m were excluded from the measurement targets.
- the number density of the holes on the surface of the Ag plating material is preferably 5,000 to 100,000 / mm 2 .
- the average diameter of the holes is preferably 1 to 30 ⁇ m, more preferably 2 to 20 ⁇ m. It was
- the thickness of the Ag plating layer is preferably 0.1 to 3 ⁇ m, more preferably 0.2 to 2 ⁇ m. With this thickness, a large number of holes can be formed in the Ag plating layer after appropriately setting the number density of the holes and the average diameter of the holes. If it is thicker than 3 ⁇ m, the pores on the surface of the porous Ni plating layer may be filled with the Ag plating layer, and a large number of pores may not be sufficiently formed on the surface.
- the above numerical range is an example, and after all, the thickness of the Ag plating layer may be any thickness as long as a large number of holes are formed on the upper surface of the Ag plating layer.
- the thickness of any Ag plating layer constituting the Ag plating material is more preferably a thickness at which a large number of holes are formed on the upper surface of the Ag plating layer, specifically 0.2 to 2 ⁇ m. Is more preferable, and 0.5 ⁇ m or more is further preferable.
- the Ag plating material of the present embodiment has excellent wear resistance, and preferably has excellent vibration resistance.
- a base Ni plating layer is further formed between the two-layer plating structure on the base material side and the base material.
- the base Ni plating layer By forming the base Ni plating layer, for example, when the Ag plating material is heated, elements such as Cu and Fe, which are components of the base material, are prevented from diffusing into the Ag plating layer, and the base material and porous Ni are prevented from diffusing. It is possible to suppress deterioration of characteristics such as deterioration of adhesion to the plating layer.
- the thickness of the underlying Ni plating layer is preferably 0.05 to 2 ⁇ m.
- the method for producing the Ag plating material of the present embodiment is a method for producing an Ag plating material in which an Ag plating layer is formed on a base material made of a conductive metal, and the base material side is placed on the base material. Therefore, it is characterized in that a two-layer plating structure having a porous Ni plating layer and an Ag plating layer in this order is formed, and a plurality of these two-layer plating structures are formed.
- the contents not described below are the same as the contents described in the item of ⁇ Ag plating material>.
- Step 1 Pretreatment step
- the base material is a cathode and a separately prepared SUS plate is used as an anode, and electrolytic degreasing is performed to remove organic substances on the base material. Then, it is preferable to pickle the substrate with an aqueous solution containing an acid such as sulfuric acid.
- Step 2 Base Ni plating layer forming step
- the composition (composition) and plating conditions of the plating bath for forming the base Ni plating layer are not limited, and the plating baths (sulfamic acid bath; nickel sulfamate and borate, nickel chloride) listed in the items of Examples described later are not limited. Etc.) and plating conditions can be used.
- Examples of other plating baths include a watt bath (consisting of nickel sulfate and nickel chloride, boric acid and the like) and a total chloride bath (consisting of nickel chloride and boric acid and the like).
- the Ni concentration in the base Ni plating solution is preferably 5 to 200 g / L, more preferably 10 to 180 g / L, and most preferably 20 to 150 g / L, and such plating. It is preferable to perform electroplating using a liquid.
- the liquid temperature of the plating solution for forming the underlying Ni plating layer is preferably 10 to 70 ° C, more preferably 25 to 55 ° C.
- the current density is preferably 15 A / dm 2 or less, more preferably 10 A / dm 2 or less, and further preferably 0.5 to 7 A / dm 2 .
- Step 3 Porous Ni plating layer forming step It is preferable to form a porous Ni plating layer directly above the underlying Ni plating layer. There are no restrictions on the composition (composition) and plating conditions of the plating bath (liquid) when forming the porous Ni plating layer, and plating is performed in a plating bath containing Ni ions, and porous plating containing Ni as the main component. Any layer may be formed.
- a method of electroplating in a plating bath containing a Ni ion and a water-soluble quaternary ammonium salt having a hydrophobic group is exemplified.
- the quaternary ammonium salt can be added to a known Ni electroplating bath.
- Examples of known electroplating baths include watt baths, ni sulfamic acid baths, and nickel organic acid baths.
- the Ni concentration in this porous Ni plating solution is preferably 5 to 200 g / L, more preferably 10 to 180 g / L, and most preferably 20 to 150 g / L.
- the liquid temperature of the plating solution for forming the porous Ni plating layer is preferably 10 to 70 ° C, more preferably 25 to 55 ° C.
- the current density is preferably 15 A / dm 2 or less, more preferably 10 A / dm 2 or less, and further preferably 0.5 to 7 A / dm 2 .
- Step 4 Ag strike plating layer forming step It is preferable to form an Ag strike plating layer directly above the porous Ni plating layer.
- the configuration and plating conditions of the plating bath when forming the Ag strike plating layer are not limited, and known plating baths and plating conditions can be applied. In addition, the plating baths and plating conditions listed in the items of the examples below can be used.
- the Ag concentration in this Ag strike plating solution is preferably 0.01 to 15 g / L, more preferably 0.1 to 10 g / L, and most preferably 0.2 to 5 g / L. .. Further, it is preferable to perform Ag strike plating by electroplating.
- the liquid temperature of the plating solution for forming the Ag strike plating layer is preferably 10 to 60 ° C, more preferably 15 to 55 ° C.
- the current density is preferably 8 A / dm 2 or less, more preferably 5 A / dm 2 or less, and further preferably 0.2 to 3 A / dm 2 .
- Step 5 Ag main plating layer forming step It is preferable to form the Ag main plating layer directly above the Ag strike plating layer.
- the composition and plating conditions of the plating bath for forming the Ag main plating layer are not limited, and the plating bath and plating conditions listed in the item of Examples described later can be used.
- the thickness of the Ag main plating layer may be set to a thickness at which a large number of holes are formed in the Ag main plating layer, and is preferably formed by electroplating.
- the Ag concentration in this Ag main plating solution is preferably 5 to 200 g / L, more preferably 20 to 180 g / L, and most preferably 50 to 150 g / L.
- the liquid temperature of the plating solution for forming the Ag main plating layer is preferably 10 to 60 ° C, more preferably 15 to 55 ° C.
- the current density is preferably 15 A / dm 2 or less, more preferably 10 A / dm 2 or less, and further preferably 0.5 to 7 A / dm 2 .
- the Ag strike plating layer and the Ag main plating layer formed on the Ag strike plating layer have a very thin Ag strike plating layer even when the cross section of the Ag plating material is observed with a microscope, and the composition is also Ag. Since it is difficult to distinguish, it is regarded as one Ag-plated layer.
- an electric component such as a switch, a connector, a contact or a terminal component is manufactured using the Ag plating material of the present embodiment as a material, an electronic component having excellent wear resistance and vibration resistance can be obtained.
- Example 1 Pretreatment (electrolytic degreasing and pickling)
- a 67 mm ⁇ 50 mm ⁇ 0.3 mm pure copper metal plate C1020
- this base material and a separately prepared SUS plate are placed in an alkaline degreasing solution, and the base material is used as a cathode and the SUS plate is used as an anode.
- the substrate was pickled in a 3% aqueous sulfuric acid solution for 15 seconds. A 15-second wash was performed between each operation.
- Step 2 Formation of base Ni plating layer
- a plating solution consisting of an aqueous solution containing 540 g / L of nickel sulfamic acid tetrahydrate, 25 g / L of nickel chloride and 35 g / L of boric acid was prepared.
- the base material is a cathode and a separately prepared SK (sulfur-containing) nickel electrode plate is used as an anode, and while stirring with a magnetic stirrer at 500 rpm, electricity is applied at a current density of 7 A / dm 2 and a liquid temperature of 50 ° C.
- Plating was performed to form a base Ni plating layer having a thickness of 0.2 ⁇ m directly above the substrate.
- Step 3 Formation of porous Ni plating layer
- 10 mL / L top as an additive for nickel plating that can obtain a nickel plating film with 540 g / L nickel sulfamate tetrahydrate, 25 g / L nickel chloride, 35 g / L boric acid and a porous structure.
- a plating solution consisting of an aqueous solution containing porous nickel RSN (manufactured by Okuno Pharmaceutical Co., Ltd.) was prepared. The total amount of the plating solution was 1 L.
- the base material on which the base Ni plating layer is formed (hereinafter, the intermediate is referred to as "material to be plated”) is used as a cathode, and the SK nickel electrode plate is used as an anode, and the mixture is stirred at 500 rpm by a magnetic stirrer.
- electroplating is performed at a current density of 1 A / dm 2 and a liquid temperature of 50 ° C. for 500 seconds so that a volume of Ni corresponding to a non-porous Ni plating layer having a thickness of 1 ⁇ m (set value) is formed.
- a porous Ni plating layer was formed directly above the plating layer. The thickness of the porous Ni plating layer (set value above) at that time is shown in Table 1 below.
- the material after forming the porous Ni-plated layer use a fluorescent X-ray film thickness meter (FT-110A manufactured by Hitachi High-Tech Science Co., Ltd.), and use a collimator diameter of ⁇ 0.2 mm and a measurement time of 10 sec to cover the Ni-plated layer in the center of the sample. As a result of measuring the thickness, it was confirmed that the film thickness was 1.2 ⁇ m and the film thickness was as set. From the measurement principle of the fluorescent X-ray film thickness meter, it is considered that the sum of the thicknesses of the underlying Ni plating layer and the porous Ni plating layer is measured as the thickness of the Ni plating layer.
- FT-110A manufactured by Hitachi High-Tech Science Co., Ltd.
- Step 4 Formation of Ag strike plating layer
- a plating solution consisting of an aqueous solution containing 3 g / L of silver cyanide and 90 g / L of potassium cyanide was prepared.
- the material to be plated is used as a cathode and a titanium electrode plate coated with platinum is used as an anode, and while stirring with a magnetic stirrer at 500 rpm, electroplating is performed at a liquid temperature of 25 ° C. and the current density shown in the table for 10 seconds. After that, it was washed with water for 15 seconds.
- Step 5 Formation of Ag main plating layer
- a silver plating bath consisting of an aqueous solution containing 175 g / L of silver cyanide, 95 g / L of potassium cyanide and 6 mg / L of selenium was prepared.
- an Ag plating layer having a thickness of 1 ⁇ m (set value) is formed while stirring with a magnetic stirrer at 500 rpm using the material to be plated as a cathode and a silver electrode plate having a purity of 99.99% or more as an anode.
- Electroplating was performed for 240 seconds at a current density of 0.5 A / dm 2 and a liquid temperature of 18 ° C.
- the thickness of the Ag plating layer in Table 1 is the total thickness (the above set value) of the Ag strike plating layer and the Ag main plating layer. After forming the Ag main plating layer, it was washed with water for 15 seconds.
- a fluorescent X-ray film thickness meter (FT-110A manufactured by Hitachi High-Tech Science Co., Ltd.) was used, the collimator diameter was ⁇ 0.2 mm, and the measurement time was 10 sec. As a result of measuring the plating, it was confirmed that the film thickness was 1 ⁇ m and the film thickness was as set.
- step 3) to (step 5) (set) were repeated twice to prepare an Ag plating material consisting of a total of 7 plating layers including the base Ni plating layer (Ag strike plating layer is Ag main plating). Counted as one layer together with the layers).
- the thickness of each layer of the produced Ag plating material was adjusted to an acceleration voltage of 10 kV, irradiation current of 1 ⁇ 10 -7 A, and beam diameter. Under the condition of 100 ⁇ m ⁇ , Ag and Ni are measured while etching the surface of the Ag plating material in the depth direction by Ar sputtering (acceleration voltage 3 kV, emission current 25 mA), and the plating thickness is calculated from the depth direction profile of Ag and Ni. did.
- the measurement data step interval was 0.5 minutes between 0 and 300 seconds, 1 minute between 300 and 600 seconds, and 2 minutes when 600 seconds or more.
- a measurement example is shown in FIG.
- a method for calculating the plating film thickness will be described.
- the horizontal axis is the sputtering time, and the vertical axis is the concentration (atomic percentage) of Ag and Ni in the depth direction profiles (depth profiles). do.
- the intermediate point on the side where the sputter time is smaller than the minimum value closest to the surface (the outermost surface side) is adjacent to the minimum value and the spatter time is large.
- the same concentration as the midpoint plotted in is plotted on the moving average line (between the local minimum and the outermost surface) to be the midpoint.
- the midpoint on the side where the sputter time is larger than the maximum value closest to the base material (base material side) is adjacent to the maximum value and the spatter time is short.
- the same concentration as the midpoint plotted on the side is plotted on the moving average line (between the maximum value and the base material side) to be the midpoint.
- the midpoint on the side with the smaller sputter time (outermost surface side) than the maximum value closest to the surface is plotted on the side with the larger sputter time adjacent to the maximum value.
- the same concentration as the midpoint is plotted on the moving average line (between the maximum value and the outermost surface) to be the midpoint.
- the midpoint on the side with the larger sputter time (base material side) than the maximum value closest to the base material is plotted on the side with the smaller spatter time adjacent to the maximum value.
- the same concentration as the intermediate point is plotted on the moving average line (between the maximum value and the substrate side) to be the intermediate point.
- the adjacent intermediate points are connected by a line, and the length (plating time) in the horizontal axis direction of the section where the maximum value comes to the upper side of this line is measured.
- This length was converted into a thickness from the etching rate of SiO 2 (etching rate 20 nm / min), and was used as the plating thickness of each of the Ag plating layer and the Ni plating layer.
- the thickness of the Ag plating layer was determined by converting with the above etching rate.
- the plating thickness specified in the claims of the present invention is calculated by such a method.
- the thickness of the Ag plating layer (7 layers) was 0.611 ⁇ m
- the thickness of the porous Ni plating layer (6 layers) was 1.148 ⁇ m
- the thickness of the Ag plating layer (5 layers) The thickness of the porous Ni plating layer (4 layers) is 1.453 ⁇ m
- the thickness of the Ag plating layer (3 layers) is 0.69 ⁇ m
- the thickness of the porous Ni plating layer (2 layers). was 1.099 ⁇ m.
- the Ag plating material of Example 1 had no exposure of the copper substrate even after 1,000 sliding times, had a contact resistance of less than 1 m ⁇ , and was excellent in wear resistance.
- the Ag plating material of Example 1 had a contact resistance of less than 1 m ⁇ even after 50,000 sliding times, and was excellent in vibration resistance.
- the height with the largest area detected is the surface (calculated by the analysis application), and no object (plating surface) is detected at a distance (position) of 0.5 ⁇ m in the depth direction from the surface.
- the part is regarded as a hole (porous part), and the number and area of the holes are measured.
- the average area of the holes was calculated from the measured number of holes and the area of the holes, and the diameter of a circle having the same area as the average area of the holes was calculated to obtain the average diameter of the holes.
- the number density of holes per unit area was calculated from the measurement results.
- the number density of the holes was 9,300 / mm 2 , and the average diameter of the holes was 16.3 ⁇ m.
- Example 2 the composition of the Ni plating solution for porous Ni plating is 540 g / L of nickel sulfamate tetrahydrate, 25 g / L of nickel chloride, 35 g / L of boric acid, and nickel plating of a porous structure.
- a plating solution consisting of an aqueous solution containing 175 g / L of silver potassium cyanide, 95 g / L of potassium cyanide and 55 mg / L of selenium was prepared, and in the step of forming the Ag main plating layer, the material to be plated was used as a cathode and the purity was 99.99.
- a silver electrode plate of mass% or more as an anode, while stirring with a stirrer at 500 rpm, electroplating for 24 seconds with a current density of 5 A / dm 2 and a liquid temperature of 18 ° C so that an Ag plating layer with a thickness of 1 ⁇ m is formed.
- the Ag plating material was prepared by the same method as in Example 1 except that the Ag main plating layer was formed.
- the thickness of the Ag plating layer (7 layers) is 0.613 ⁇ m in order from the surface side of the Ag plating material, and porous Ni plating.
- the thickness of the layer (6 layers) is 0.998 ⁇ m
- the thickness of the Ag plating layer (5 layers) is 0.825 ⁇ m
- the thickness of the porous Ni plating layer (4 layers) is 1.384 ⁇ m
- the thickness of the Ag plating layer (3 layers). ) was 0.637 ⁇ m
- the thickness of the porous Ni-plated layer (2 layers) was 1.415 ⁇ m.
- the contact resistance was less than 1 m ⁇ even after sliding 50,000 times, and the vibration resistance was excellent.
- Example 3 The Ag plating material was produced by the same method as in Example 2 except that (Step 3) to (Step 5) (set) were repeated once to form a total of 5 layers.
- the contact resistance was less than 1 m ⁇ even after sliding 13,000 times, and the vibration resistance was excellent. (The contact resistance after sliding 20,000 times exceeded 1 m ⁇ .)
- Example 4 The Ag plating material was produced by the same method as in Example 2 except that (Step 3) to (Step 5) (set) were repeated 3 times to form a total of 9 layers.
- the contact resistance was less than 1 m ⁇ even after sliding 50,000 times, and the vibration resistance was excellent.
- Example 5 An Ag plating material was produced by the same method as in Example 2 except that the electroplating time for porous Ni plating was 250 seconds and the electroplating time for Ag main plating was 12 seconds.
- the thickness of the Ag plating layer (7 layers) is 0.439 ⁇ m in order from the surface side of the Ag plating material, and porous Ni plating.
- the thickness of the layer (6 layers) is 0.425 ⁇ m
- the thickness of the Ag plating layer (5 layers) is 0.463 ⁇ m
- the thickness of the porous Ni plating layer (4 layers) is 0.561 ⁇ m
- the thickness of the Ag plating layer (3 layers). ) was 0.386 ⁇ m
- the thickness of the porous Ni-plated layer (2 layers) was 0.439 ⁇ m.
- the contact resistance was less than 1 m ⁇ even after sliding 20,000 times, and the vibration resistance was excellent. (The contact resistance after sliding 30,000 times exceeded 1 m ⁇ .)
- Example 6 An Ag plating material was produced by the same method as in Example 4 except that the electroplating time for porous Ni plating was 250 seconds and the electroplating time for Ag main plating was 12 seconds.
- the contact resistance was less than 1 m ⁇ even after sliding 50,000 times, and the vibration resistance was excellent.
- Example 7 An Ag plating material was produced by the same method as in Example 3 except that the electroplating time for porous Ni plating was 250 seconds and the electroplating time for Ag main plating was 12 seconds.
- the contact resistance was less than 1 m ⁇ even after sliding 10,000 times, and the vibration resistance was excellent. (The contact resistance after sliding 15,000 times exceeded 1 m ⁇ .)
- Comparative Example 1 an Ag plating material was produced by the same method as in Example 2 except that only one two-layer plating structure was used (a total of three layers without repeating (Step 3) to (Step 5)). ..
- Example 2 Same as Example 1 except that the two-layer plating structure is only one (three layers in total without repeating (step 3) to (step 5)) and the electroplating time of this Ag plating is 720 seconds. By the method, an Ag plating material was produced.
- Example 3 Same as Example 1 except that the two-layer plating structure is only one (three layers in total without repeating (step 3) to (step 5)) and the electroplating time of this Ag plating is 1,200 seconds.
- the Ag plating material was produced by the above method.
- the two-layer plating structure is only one (three layers in total without repeating (step 3) to (step 5)), the electroplating time for porous Ni plating is 1,500 seconds, and the electroplating time for this Ag plating is 720.
- the Ag plating material was produced by the same method as in Example 1 except that the number of seconds was set.
- Comparative Example 7 In Comparative Example 7, the base Ni plating was not provided, the additive (top porous nickel RSN) was not added to the Ni plating solution of step 3 of the first embodiment (that is, the porous Ni plating layer was not provided), and the thickness was 1 ⁇ m.
- the Ni-plated layer of No. 1 was formed, and an Ag-plated material was produced by the same method as in Example 1 except that the current density of Ag-strike plating was 2 A / dm 2 .
- Comparative Example 8 In Comparative Example 8, the base Ni plating layer was not provided, and no additive (top porous nickel RSN) was added to the Ni plating solution of step 3 of Example 1 (that is, no porous Ni plating layer was provided). Except for forming a 1 ⁇ m Ni plating layer and forming only one 5 ⁇ m thick Ag plating layer on it with an Ag strike plating current density of 2 A / dm 2 and an Ag main plating time of 120 seconds. An Ag plating material was prepared in the same manner as in Example 2.
- FIG. 1 is a secondary electron image (2000 times) of the surface of the Ag plating material of Example 1 by SEM (scanning electron microscope).
- FIG. 2 is a SIM (scanning ion microscope) image of a cross section of the Ag plating material of Example 1.
- FIG. 3 is a SIM image of a cross section of the Ag plating material of Example 5.
- FIG. 4 is a secondary electron image (2000 times) of the surface of the Ag plating material of Comparative Example 2 by SEM.
- FIG. 5 is a secondary electron image (2000 times) of the surface of the Ag plating material of Comparative Example 3 by SEM.
- FIG. 6 is a secondary electron image (2000 times) of the surface of the Ag plating material of Comparative Example 4 by SEM.
- FIG. 1 is a secondary electron image (2000 times) of the surface of the Ag plating material of Example 1 by SEM (scanning electron microscope).
- FIG. 2 is a SIM (scanning ion microscope) image of a cross section of the
- FIG. 7 is a secondary electron image (2000 times) of the surface of the Ag plating material of Comparative Example 6 by SEM.
- FIG. 8 is a SIM image of a cross section of the Ag plating material of Comparative Example 7.
- FIG. 9A is a secondary electron image (2000 times) of the surface of the Ag plating material of Example 1 by EPMA (electron probe microanalyzer).
- FIG. 9B is a reflected electron composition image (2000 times) of the surface of the Ag plating material by EPMA (electron probe microanalyzer).
- FIG. 9 (c) is a characteristic X-ray image of Ag by WDX (wavelength dispersive X-ray spectroscopy) by EPMA (electron probe microanalyzer) on the surface of the Ag plating material.
- FIG. 9D is a characteristic X-ray image of Ni by WDX (wavelength dispersive X-ray spectroscopy) by EPMA (electron probe microanalyzer) on the surface of the Ag plating material.
- FIG. 10A is a secondary electron image (2000 times) of the surface of the Ag plating material of Example 1 after the wear resistance test by EPMA (electron probe microanalyzer).
- FIG. 10 (b) is a reflected electron composition image (2000 times) of the surface of the Ag plating material after the wear resistance test by EPMA (electron probe microanalyzer).
- FIG. 10A is a secondary electron image (2000 times) of the surface of the Ag plating material of Example 1 after the wear resistance test by EPMA (electron probe microanalyzer).
- FIG. 10 (b) is a reflected electron composition image (2000 times) of the surface of the Ag plating material after the wear resistance test by EPMA (electron probe microanalyzer).
- FIG. 10A
- FIG. 10 (c) is a characteristic X-ray image of Ag by WDX (wavelength dispersive X-ray spectroscopy) by EPMA (electron probe microanalyzer) on the surface of the Ag plating material after the wear resistance test.
- FIG. 10D is a characteristic X-ray image of Ni by WDX (wavelength dispersive X-ray spectroscopy) by EPMA (electron probe microanalyzer) on the surface of the Ag plating material after the wear resistance test.
- Example 1 As shown in FIG. 1, in Example 1, a large number of holes are formed on the surface of the Ag plating material.
- Example 1 As shown in FIG. 2, in Example 1, it was confirmed that a two-layer plating structure having a porous Ni plating layer and an Ag plating layer in this order was formed, and three sets of these two-layer plating structures were provided. can. In addition, a large number of holes can be confirmed on the surface of the porous Ni plating layer other than the outermost surface side of the Ag plating material, and it can be seen that each Ag plating layer provided directly above each porous Ni plating layer has entered the holes. You can check it. The situation can also be confirmed in FIG. 3, which shows a SIM image of a cross section of the Ag plating material according to the fifth embodiment.
- FIG. 10 (c) after the wear resistance test of the Ag plating material is performed, Ag is confirmed in the white part of the image of FIG. 10 (b), and it can be seen that Ag plating remains. ..
- FIG. 10 (d) in the black portion of the image of FIG. 10 (b), a portion having a higher Ni concentration was observed in a mesh pattern as compared with FIG. 9 (d). It is considered that a part of the soft Ag plating layer on the surface was scraped by the sliding test and a part of the porous Ni plating layer was exposed, and such a mesh pattern was observed.
- the purity of Ni in the Ni plating layer and the porous Ni plating layer of Examples and Comparative Examples is 99% by mass or more, and the purity of Ag in the Ag strike plating layer and the Ag main plating layer is 99% by mass or more. Is.
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Abstract
Description
このような高圧端子に求められる特性として、耐挿抜性と耐摩耗性(本明細書ではまとめて耐摩耗性と呼称する。)があり、好適には微摺動摩耗に耐えるための性能(耐振動性)がある。
導電性金属からなる基材の上にAgめっき層が形成されたAgめっき材であって、
前記基材の上に、基材側から、ポーラスNiめっき層とAgめっき層とをこの順序で有する2層のめっき構造が形成され、この2層のめっき構造を複数備えている、Agめっき材である。
最も基材側にある前記2層のめっき構造と前記基材との間に、下地Niめっき層が更に形成されている。
前記下地Niめっき層の厚さが0.05~2μmである。
前記Agめっき材の表面に多数の孔が形成されてなる。
前記孔の個数密度が5000~100,000個/mm2である。
前記孔の平均直径が1~10μmである。
前記ポーラスNiめっき層の厚さが0.1~3μmである。
前記Agめっき層の厚さが0.1~3μmである。
導電性金属からなる基材の上にAgめっき層が形成されたAgめっき材の製造方法であって、
前記基材の上に、基材側から、ポーラスNiめっき層とAgめっき層とをこの順序で有する2層のめっき構造を形成し、この2層のめっき構造を複数形成する、Agめっき材の製造方法である。
最も基材側にある前記2層のめっき構造と前記基材との間に、下地Niめっき層を更に形成する。
前記下地Niめっき層の厚さを0.05~2μmとする。
前記ポーラスNiめっき層の厚さを0.1~3μmとする。
前記Agめっき層の厚さを0.1~3μmとする。
第1~第8のいずれか一つの態様に記載のAgめっき材を材料として用いた接点又は端子部品である、電気部品である。
本実施形態に係るAgめっき材は、導電性金属からなる基材の上にAgめっき層が形成されたAgめっき材であって、前記基材の上に、基材側(下側)から、ポーラスNi(ニッケル)めっき層とAg(銀)めっき層とをこの順序で有する2層のめっき構造が形成され、この2層のめっき構造を複数備えていることを特徴とする。
本実施形態のAgめっき材の製造方法としては、導電性金属からなる基材の上にAgめっき層が形成されたAgめっき材の製造方法であって、前記基材の上に、基材側から、ポーラスNiめっき層とAgめっき層とをこの順序で有する2層のめっき構造を形成し、この2層のめっき構造を複数形成することを特徴とする。以下に記載の無い内容は、<Agめっき材>の項目に記載の内容と同様とする。
前処理として、基材に対する電解脱脂および酸洗を行うのが好ましい。例えば、基材を陰極、別途用意したSUS板を陽極とし、電解脱脂を行い、基材上の有機物を除去するのが好ましい。その後、硫酸などの酸を含む水溶液により基材を酸洗するのが好ましい。
次に、下地Niめっき層を形成するのが好ましい。下地Niめっき層を形成する際のめっき浴の構成(組成)およびめっき条件には限定は無く、後掲の実施例の項目で挙げるめっき浴(スルファミン酸浴;スルファミン酸ニッケルとホウ酸、塩化ニッケル等からなる)およびめっき条件を使用可能である。他のめっき浴としては、ワット浴(硫酸ニッケルと塩化ニッケル、ホウ酸等からなる)、全塩化物浴(塩化ニッケルとホウ酸等からなる)が挙げられる。
下地Niめっき層の直上に、ポーラスNiめっき層を形成するのが好ましい。ポーラスNiめっき層を形成する際のめっき浴(液)の構成(組成)およびめっき条件には限定は無く、Niイオンを含有するめっき浴中でめっきを施し、Niを主成分とする多孔質めっき層が形成されるのであればよい。
ポーラスNiめっき層の直上に、Agストライクめっき層を形成するのが好ましい。Agストライクめっき層を形成する際のめっき浴の構成およびめっき条件には限定は無く、公知のめっき浴、めっき条件を適用できる。また、後掲の実施例の項目で挙げるめっき浴およびめっき条件を使用可能である。
Agストライクめっき層の直上に、Ag本めっき層を形成するのが好ましい。Ag本めっき層を形成する際のめっき浴の構成およびめっき条件には限定は無く、後掲の実施例の項目で挙げるめっき浴およびめっき条件を使用可能である。Ag本めっき層の厚さは、Ag本めっき層に多数の孔が形成される厚さに設定すればよく、電気めっきにより形成することが好ましい。
まず、基材として67mm×50mm×0.3mmの純銅金属板(C1020)を用意し、この基材と別途用意したSUS板とをアルカリ脱脂液に入れ、基材を陰極、SUS板を陽極とし、電圧5Vで30秒間電解脱脂した。その後、3%硫酸水溶液中で15秒間、基材を酸洗した。各作業間では15秒の水洗を実施した。
次に、540g/Lのスルファミン酸ニッケル四水和物と25g/Lの塩化ニッケルと35g/Lのホウ酸を含む水溶液からなるめっき液(浴)を用意した。そして該めっき液中において、基材を陰極、別途用意したSK(硫黄含有)ニッケル電極板を陽極とし、マグネチックスターラにより500rpmで撹拌しつつ、電流密度7A/dm2、液温50℃で電気めっきを行い、基材の直上に0.2μmの厚さの下地Niめっき層を形成した。
次に、540g/Lのスルファミン酸ニッケル四水和物と25g/Lの塩化ニッケルと35g/Lのホウ酸と多孔性構造のニッケルめっき皮膜が得られるニッケルめっき用添加剤として10mL/LのトップポーラスニッケルRSN(奥野製薬工業株式会社製)を含む水溶液からなるめっき液を用意した。めっき液の総量は1Lとした。
次に、3g/Lのシアン化銀カリウムと90g/Lのシアン化カリウムを含む水溶液からなるめっき液を用意した。そして該めっき液中において、被めっき材を陰極、白金で被覆したチタン電極板を陽極とし、マグネチックスターラにより500rpmで撹拌しつつ、液温25℃、表に記載の電流密度で10秒間電気めっきを行った後、15秒間水洗した。
次に、175g/Lのシアン化銀カリウムと95g/Lのシアン化カリウムと6mg/Lのセレンを含む水溶液からなる銀めっき浴を用意した。該めっき浴中において、被めっき材を陰極、純度99.99%以上の銀電極板を陽極とし、マグネチックスターラにより500rpmで撹拌しつつ、厚さ1μm(設定値)のAgめっき層が形成されるように電流密度0.5A/dm2、液温18℃で240秒間電気めっきを行い、Agストライクめっき層の直上にAg本めっき層を形成した。表1のAgめっき層の厚さはAgストライクめっき層とAg本めっき層との合計厚さ(上記設定値)である。Ag本めっき層の形成後、15秒間水洗した。
作製したAgめっき材の各層のめっきの膜厚を、オージェ電子分光装置(日本電子株式会社製のオージェマイクロプローブJAMP-7800)を用い、加速電圧10kV、照射電流1×10-7A、ビーム径100μmφの条件で、Agめっき材の表面をArスパッタリング(加速電圧3kV、エミッション電流25mA)により深さ方向にエッチングしながらAgとNiについて測定し、AgとNiの深さ方向プロファイルよりめっき厚を算出した。測定データステップ間隔は、0~300秒の間では0.5分、300~600秒の間では1分、600秒以上では2分とした。
本発明の請求項に規定するめっきの厚さはこのような方法で算出する。
作製した銀めっき材の耐摩耗性を評価するために、株式会社山崎精機研究所製 精密摺動試験機CRS-G2050-DWA型を使用し、銀めっき材の一方を内径R=1.5mmのエンボス状(半球面状)に加工し、他方の(同じ平板状の)銀めっき材の板面上に荷重5Nで接触させたのち、摺動速度1.67mm/sec、摺動距離5mmで往復摺動をし、銅素地が露出するまでの回数を測定した。ただし接触抵抗が1mΩを超えた場合、その時点でNGとした。
作製した銀めっき材の耐摩耗性を評価するために、株式会社山崎精機研究所製 精密摺動試験機CRS-G2050-DWA型を使用し、銀めっき材の一方を内径R=1.5mmのエンボス状(半球面状)に加工し、他方の(同じ平板状の)銀めっき材の板面上に荷重5Nで接触させたのち、摺動速度0.2mm/sec、摺動距離0.1mmで往復摺動をし、接触抵抗が1mΩ以上になるまでの回数を測定した。
Agめっき材の表面に観察される孔について、個数密度および平均直径を評価した。
実施例2では、ポーラスNiめっきの際のNiめっき液の組成として、540g/Lのスルファミン酸ニッケル四水和物と25g/Lの塩化ニッケルと35g/Lのホウ酸と多孔性構造のニッケルめっき皮膜が得られるニッケルめっき用添加剤として8mL/LのトップポーラスニッケルRSN(奥野製薬工業株式会社製)を含む水溶液からなるめっき液を使用し、Ag本めっきの際のAgめっき液の組成として、175g/Lのシアン化銀カリウムと95g/Lのシアン化カリウムと55mg/Lのセレンを含む水溶液からなるめっき液を用意し、Ag本めっき層の形成工程において、被めっき材を陰極、純度99.99質量%以上の銀電極板を陽極として、スターラにより500rpmで撹拌しつつ、厚さ1μmのAgめっき層が形成されるように電流密度を5A/dm2、液温を18℃として24秒間電気めっきを行いAg本めっき層を形成した、以外は実施例1と同様の方法でAgめっき材を作製した。
(工程3)~(工程5)(のセット)を1回繰り返し、合計5層とした以外は、実施例2と同様の方法でAgめっき材を作製した。
(工程3)~(工程5)(のセット)を3回繰り返し、合計9層とした以外は、実施例2と同様の方法でAgめっき材を作製した。
ポーラスNiめっきの電気めっきの時間を250秒、Ag本めっきの電気めっきの時間を12秒とした以外は、実施例2と同様の方法でAgめっき材を作製した。
ポーラスNiめっきの電気めっきの時間を250秒、Ag本めっきの電気めっきの時間を12秒とした以外は、実施例4と同様の方法でAgめっき材を作製した。
ポーラスNiめっきの電気めっきの時間を250秒、Ag本めっきの電気めっきの時間を12秒とした以外は、実施例3と同様の方法でAgめっき材を作製した。
比較例1は、2層のめっき構造を1つのみ((工程3)~(工程5)を繰り返さず合計3層)とした以外は実施例2と同様の方法で、Agめっき材を作製した。
2層のめっき構造を1つのみ((工程3)~(工程5)を繰り返さず合計3層)とし、本Agめっきの電気めっきの時間を720秒とした以外は、実施例1と同様の方法で、Agめっき材を作製した。
2層のめっき構造を1つのみ((工程3)~(工程5)を繰り返さず合計3層)とし、本Agめっきの電気めっき時間を1,200秒とした以外は、実施例1と同様の方法で、Agめっき材を作製した。
ポーラスNiめっき形成時の電流密度を3A/dm2、電気めっき時間を165秒とし、Agストライクめっき形成時の電流密度を2A/dm2、2層のめっき構造を1つのみ((工程3)~(工程5)を繰り返さず合計3層)とし、本Agめっきの電気めっき時間を1200秒とした以外は、実施例1と同様の方法で、Agめっき材を作製した。
ポーラスNiめっき形成時の電流密度5A/dm2、電気めっき時間を100秒とした以外は、比較例4と同様の方法で、Agめっき材を作製した。
2層のめっき構造を1つのみ((工程3)~(工程5)を繰り返さず合計3層)とし、ポーラスNiめっきの電気めっき時間を1,500秒、本Agめっきの電気めっき時間を720秒とした以外は、実施例1と同様の方法で、Agめっき材を作製した。
比較例7では、下地Niめっきを設けず、前記実施例1の工程3のNiめっき液に添加剤(トップポーラスニッケルRSN)を添加せず(すなわちポーラスNiめっき層を設けず)に厚さ1μmのNiめっき層を形成し、Agストライクめっきの電流密度を2A/dm2とした以外は実施例1と同様の方法で、Agめっき材を作製した。
比較例8では、下地Niめっき層を設けず、前記実施例1の工程3のNiめっき液に添加剤(トップポーラスニッケルRSN)を添加せず(すなわちポーラスNiめっき層を設けず)に厚さ1μmのNiめっき層を形成し、この上にAgストライクめっきの電流密度を2A/dm2、Ag本めっきの時間を120秒として厚さ5μmのAgめっき層を1層のみ形成した以外は、実施例2と同様の方法でAgめっき材を作製した。
図2は、実施例1のAgめっき材の断面のSIM(走査イオン顕微鏡)像である。
図3は、実施例5のAgめっき材の断面のSIM像である。
図4は、比較例2のAgめっき材の表面のSEMによる二次電子像(2000倍)である。
図5は、比較例3のAgめっき材の表面のSEMによる二次電子像(2000倍)である。
図6は、比較例4のAgめっき材の表面のSEMによる二次電子像(2000倍)である。
図7は、比較例6のAgめっき材の表面のSEMによる二次電子像(2000倍)である。
図8は、比較例7のAgめっき材の断面のSIM像である。
図9(a)は、実施例1のAgめっき材の表面のEPMA(電子プローブマイクロアナライザ)による二次電子像(2000倍)である。
図9(b)は、Agめっき材の表面のEPMA(電子プローブマイクロアナライザ)による反射電子組成像(2000倍)である。
図9(c)は、Agめっき材の表面のEPMA(電子プローブマイクロアナライザ)によるWDX(波長分散X線分光法)によるAgの特性X線像である。
図9(d)は、Agめっき材の表面のEPMA(電子プローブマイクロアナライザ)によるWDX(波長分散X線分光法)によるNiの特性X線像である。
図10(a)は、実施例1のAgめっき材に対して耐摩耗性試験後の表面のEPMA(電子プローブマイクロアナライザ)による二次電子像(2000倍)である。
図10(b)は、耐摩耗性試験後のAgめっき材の表面のEPMA(電子プローブマイクロアナライザ)による反射電子組成像(2000倍)である。
図10(c)は、耐摩耗性試験後のAgめっき材の表面のEPMA(電子プローブマイクロアナライザ)によるWDX(波長分散X線分光法)によるAgの特性X線像である。
図10(d)は、耐摩耗性試験後のAgめっき材の表面のEPMA(電子プローブマイクロアナライザ)によるWDX(波長分散X線分光法)によるNiの特性X線像である。
Claims (14)
- 導電性金属からなる基材の上にAgめっき層が形成されたAgめっき材であって、
前記基材の上に、基材側から、ポーラスNiめっき層とAgめっき層とをこの順序で有する2層のめっき構造が形成され、この2層のめっき構造を複数備えている、Agめっき材。 - 最も基材側にある前記2層のめっき構造と前記基材との間に、下地Niめっき層が更に形成されている、請求項1に記載のAgめっき材。
- 前記下地Niめっき層の厚さが0.05~2μmである、請求項2に記載のAgめっき材。
- 前記Agめっき材の表面に多数の孔が形成されてなる、請求項1~3のいずれか一つに記載のAgめっき材。
- 前記孔の個数密度が5,000~100,000個/mm2である、請求項4に記載のAgめっき材。
- 前記孔の平均直径が1~30μmである、請求項4又は5に記載のAgめっき材。
- 前記ポーラスNiめっき層の厚さが0.1~3μmである、請求項1~6のいずれか一つに記載のAgめっき材。
- 前記Agめっき層の厚さが0.1~3μmである、請求項1~7のいずれか一つに記載のAgめっき材。
- 導電性金属からなる基材の上にAgめっき層が形成されたAgめっき材の製造方法であって、
前記基材の上に、基材側から、ポーラスNiめっき層とAgめっき層とをこの順序で有する2層のめっき構造を形成し、この2層のめっき構造を複数形成する、Agめっき材の製造方法。 - 最も基材側にある前記2層のめっき構造と前記基材との間に、下地Niめっき層を更に形成する、請求項9に記載のAgめっき材の製造方法。
- 前記下地Niめっき層の厚さを0.05~2μmとする、請求項10に記載のAgめっき材の製造方法。
- 前記ポーラスNiめっき層の厚さを0.1~3μmとする、請求項9~11のいずれか一つに記載のAgめっき材の製造方法。
- 前記Agめっき層の厚さを0.1~3μmとする、請求項9~12のいずれか一つに記載のAgめっき材の製造方法。
- 請求項1~8のいずれか一つに記載のAgめっき材を材料として用いた接点又は端子部品である、電気部品。
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JP2013129902A (ja) | 2011-12-22 | 2013-07-04 | Om Sangyo Kk | めっき品及びその製造方法 |
JP2015059260A (ja) | 2013-09-20 | 2015-03-30 | 株式会社オートネットワーク技術研究所 | コネクタ用電気接点材料及びその製造方法 |
JP2017014589A (ja) | 2015-07-03 | 2017-01-19 | 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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JP2015059260A (ja) | 2013-09-20 | 2015-03-30 | 株式会社オートネットワーク技術研究所 | コネクタ用電気接点材料及びその製造方法 |
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