EP3070726B1 - Silver coating material and method for manufacturing same - Google Patents
Silver coating material and method for manufacturing same Download PDFInfo
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- EP3070726B1 EP3070726B1 EP14861043.9A EP14861043A EP3070726B1 EP 3070726 B1 EP3070726 B1 EP 3070726B1 EP 14861043 A EP14861043 A EP 14861043A EP 3070726 B1 EP3070726 B1 EP 3070726B1
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- Prior art keywords
- silver
- coated material
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- carried out
- heat treatment
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 92
- 229910052709 silver Inorganic materials 0.000 title claims description 92
- 239000004332 silver Substances 0.000 title claims description 92
- 239000000463 material Substances 0.000 title claims description 50
- 239000011248 coating agent Substances 0.000 title claims description 15
- 238000000576 coating method Methods 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000000034 method Methods 0.000 title claims description 6
- 239000010410 layer Substances 0.000 claims description 57
- 238000010438 heat treatment Methods 0.000 claims description 40
- 238000007747 plating Methods 0.000 claims description 36
- 238000005299 abrasion Methods 0.000 claims description 34
- 238000012360 testing method Methods 0.000 claims description 31
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 28
- 239000013078 crystal Substances 0.000 claims description 28
- 239000011247 coating layer Substances 0.000 claims description 8
- 229910001651 emery Inorganic materials 0.000 claims description 5
- 238000005259 measurement Methods 0.000 claims description 5
- 239000000523 sample Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 229910000906 Bronze Inorganic materials 0.000 description 4
- 229910000881 Cu alloy Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000010974 bronze Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910000640 Fe alloy Inorganic materials 0.000 description 3
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 3
- 229940098221 silver cyanide Drugs 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical group [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical group NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 2
- 229910017944 Ag—Cu Inorganic materials 0.000 description 1
- 229910017980 Ag—Sn Inorganic materials 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 241001124569 Lycaenidae Species 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 241001275902 Parabramis pekinensis Species 0.000 description 1
- 229910001370 Se alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZUPBPXNOBDEWQT-UHFFFAOYSA-N [Si].[Ni].[Cu] Chemical compound [Si].[Ni].[Cu] ZUPBPXNOBDEWQT-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 235000014987 copper Nutrition 0.000 description 1
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical class [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- UREBDLICKHMUKA-CXSFZGCWSA-N dexamethasone Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@@H](C)[C@@](C(=O)CO)(O)[C@@]1(C)C[C@@H]2O UREBDLICKHMUKA-CXSFZGCWSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 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
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
-
- 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
-
- 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
-
- 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
-
- 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
- C25D5/615—Microstructure of the layers, e.g. mixed structure
- C25D5/617—Crystalline layers
-
- 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
- H01H1/025—Composite material having copper as the basic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H11/00—Apparatus or processes specially adapted for the manufacture of electric switches
- H01H11/04—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts
- H01H11/041—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts by bonding of a contact marking face to a contact body portion
- H01H2011/046—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts by bonding of a contact marking face to a contact body portion by plating
Definitions
- This invention relates to a silver-coated material and a method of manufacture thereof. More specifically, the invention relates to a silver-coated material suitable as a contact in connectors, switches, terminals and electronic components.
- Japanese Patent Publication No. 2012-49041 discloses a silver-coated material for moving contact components which has an electrically conductive base material made of copper or a copper alloy or of iron or an iron alloy on which are superimposed, in order, an underlayer made of nickel, a nickel alloy, cobalt or a cobalt alloy, an intermediate layer made of copper, a copper alloy, tin or a tin alloy, and an outermost layer made of silver or a silver alloy, and in which an intermediate oxide layer is present as a second intermediate layer between the intermediate layer and the outermost layer.
- the intermediate oxide layer is a layer of an oxide of the metal making up the intermediate layer.
- making an intermediate oxide layer present between the intermediate layer and the outermost layer has the effect of keeping the intermediate layer ingredients from diffusing to the surface and forming an oxide within the surface layer, thus preventing a rise in the contact resistance, and moreover has the effect of suppressing peeling of the silver layer at the surface.
- the intermediate oxide layer is formed by 5 to 60 minutes of heating in open air at a temperature of 250°C after the outermost layer has been formed.
- Patent Application Publication US 2012/0301745 discloses a silver-coated material for electric contacts having a silver plating layer on a nickel underlayer, wherein crystals having a columnar structure and an average grain size of 0.5 ⁇ m are included in the plating layer.
- the object of this invention is to provide a silver-coated material of excellent abrasion resistance in which, even when used as, for example, a moving contact and/or a fixed contact in a switch used over an extended period of time under conditions where switching is repeatedly carried out, the silver or silver alloy layer at the surface does not wear away and, moreover, the contact resistance does not rise.
- the inventors have conducted extensive investigations, as a result of which they have discovered that the above problem is resolved by the use of plating to form, as an outermost layer on an electrically conductive base material, a layer made of at least silver or a silver alloy, and heat-treating under specific heating conditions. This discovery led ultimately to the present invention.
- the silver-coated material according to (1) above characterized in that the coating loss in the abrasion resistance test is less than 30 mg.
- a switch characterized by using the silver-coated material according to (1) or (2) above as a moving contact and/or fixed contact for the switch.
- a silver-coated material of excellent abrasion resistance in which the silver or silver alloy layer at the surface does not wear away and, moreover, the contact resistance does not rise even when used as, for example, a moving contact and/or a fixed contact in a switch used over an extended period of time under conditions where switching is repeatedly carried out.
- the silver-coated material of this invention is a silver-coated material that has, as an outermost layer on an electrically conductive base material, a layer made of at least silver or a silver alloy, and is characterized by having a coating loss in an abrasion resistance test of less than 40 mg, and having an initial contact resistance of less than 10 m ⁇ and a contact resistance of less than 10 m ⁇ after a sliding wear test carried out under the following conditions.
- Contact resistance measurement conditions Apparatus: Yamasaki type CRS-1 Contact Simulator Conditions: contact load, 10 g (Au probe); sliding distance, 1 mm Sliding wear test conditions: [Load] 1.6 N [Sliding range] 0.2 mm [Sliding speed] 1 mm/s [Number of cycles] 50 000, wherein, the abrasion resistance test is carried out in accordance with JIS H 8682 under conditions of a load of 4.9 N (500 gf) (surface area of abrasion, 12 mm x 31 mm), with #1500 emery paper, and 200 back-and-forth cycles.
- the conductive base material is a material having, for example, electrical conductivity, spring characteristics and durability.
- it is preferably made of copper or a copper alloy, or iron or an iron alloy.
- Copper alloys that can be preferably used include bronzes, phosphor bronzes, brasses, titanium coppers, copper-nickel-silicon (Corson) alloys and beryllium coppers.
- Iron alloys that can be preferably used include stainless steels (SUS) and Alloy 42.
- silver alloys such as Ag-Sn alloys, Ag-Cu alloys, Ag-In alloys and Ag-Se alloys have good contact characteristics and thus can be preferably used.
- the silver alloy is preferably one having a silver content in excess of 50% by mass.
- the outermost layer made of silver or a silver alloy is formed by plating using a known silver plating solution or silver alloy plating solution.
- the plating solution is not particularly limited, although a plating solution that contains cyanide as a complex is preferred. Prior to plating with a plating solution containing the cyanide as a complex, silver strike plating may be carried out. By using plating to form the outermost layer made of silver or a silver alloy, the layer can be easily and conveniently formed at a low cost.
- the outermost layer has a thickness of preferably from 0.05 to 5 ⁇ m, more preferably from 0.1 to 2 ⁇ m, and even more preferably from 0.2 to 2 ⁇ m.
- the silver-coated material of the invention may have an underlayer between the base material and the outermost layer made of silver or a silver alloy.
- the underlayer include a plated Ni layer, a plated copper layer and a plated cobalt layer. These may be formed with a known plating solution and under known plating conditions.
- the plating solution used to form an underlying plated Ni layer is preferably a sulfamate bath.
- the plating solution used to form an underlying plated copper layer is preferably a copper cyanide bath.
- Preferred silver-coated materials of the invention are ones having an outermost layer made of silver or a silver alloy on an electrically conductive base material, and ones having a plated copper or a plated Ni layer as an underlayer between an electrically conductive base material and an outermost layer made of silver or a silver alloy.
- the silver-coated material of the invention after the outermost layer has been formed, is heat-treated at 200 to 500°C for 1 to 299 seconds. At a low temperature in this temperature range, it is preferable to make the treatment time longer; at a high temperature, it is preferable to make the treatment time shorter. From the standpoint of productivity, heat treatment at 250 to 450°C for 1 to 59 seconds is preferred, heat treatment at 270 to 450°C for 1 to 30 seconds is more preferred, and heat treatment at 300 to 450°C for 1 to 10 seconds is especially preferred.
- the spherical silver or silver alloy crystal grains in the outermost layer grow, enlarging to an average crystal grain size of 0.2 ⁇ m or more and becoming columnar in the plating thickness direction, and so the outermost layer includes crystals of a columnar structure that are made of silver or a silver alloy.
- the silver-coated material of the present invention is further characterized in that the outermost layer has an average crystal grain size of 0.2 ⁇ m or more and 0.5 ⁇ m or less, and includes crystals having a columnar structure.
- heat treatment may be carried out in an inert gas atmosphere.
- heat treatment in open air is easy and desirable.
- the heating method for heat treatment is not particularly limited. Heat treatment may be carried out using, for example, a hot plate or a circulating hot-air oven.
- a silver-coated material with, as the outermost layer, a layer made of silver or a silver alloy, when heat-treated in this way, has a coating loss in an abrasion resistance test of less than 40 mg and has an initial contact resistance of less than 10 m ⁇ and a contact resistance of less than 10 m ⁇ after a sliding wear test has been carried out under the following conditions.
- a coating loss in the abrasion resistance test of less than 30 mg is more preferred.
- the coating loss can be made less than 30 mg by the heat treatment conditions.
- the abrasion resistance test was carried out in accordance with JIS H 8682 under conditions of a load of 4.9 N (500 gf) (surface area of abrasion, 12 mm ⁇ 31 mm), with #1500 emery paper, and 200 back-and-forth cycles.
- the silver-coated material of the invention has, as mentioned above, an excellent peel resistance and abrasion resistance, and the contact resistance does not rise, it can be suitably used in connectors and switches serving as connection components for electronic equipment.
- This plated substrate was heat-treated in open air using a hot plate under the Example 1 conditions in Table 1.
- the heat treatment temperature is the temperature of the plated substrate that has been set on a hot plate, as measured with a thermocouple.
- phosphor bronze C5210, 25 mm ⁇ 20 mm ⁇ 0.2 mm (T): copper plating to a thickness of 3 ⁇ m in a copper cyanide bath, silver strike plating to a thickness of 0.05 ⁇ m, and silver plating in a high silver cyanide bath to a thickness of 0.4 ⁇ m, was used as the test material.
- This plated substrate was heat-treated using a hot plate in open air under the Example 4 conditions in Table 1.
- Example 2 Aside from changing the heat treatment conditions in Example 2 to the conditions indicated in Table 1 and heating in a nitrogen atmosphere (oxygen concentration of less than 1%), a heat-treated plated substrate was obtained in the same way as in Example 2.
- Example 4 Aside from changing the heat treatment conditions in Example 4 to the conditions indicated in Table 1, a heat-treated plated substrate was obtained in the same way as in Example 4.
- Example 2 Aside from changing the heat treatment conditions in Example 2 to the conditions indicated in Table 1, a heat-treated plated substrate was obtained in the same way as in Example 2.
- Example 4 Aside from changing the heat treatment conditions in Example 4 to the conditions indicated in Table 1, a heat-treated plated substrate was obtained in the same way as in Example 4.
- Example 2 Aside from changing the heat treatment conditions in Example 2 to the conditions indicated in Table 1, a heat-treated plated substrate was obtained in the same way as in Example 2.
- Example 1 Aside from changing the heat treatment conditions in Example 1 to the conditions indicated in Table 1, a heat-treated plated substrate was obtained in the same way as in Example 1.
- Example 4 Aside from changing the heat treatment conditions in Example 4 to the conditions indicated in Table 1, heat-treated plated substrates were obtained in the same way as in Example 4.
- Abrasion resistance tests were carried out on the heat-treated plated substrates.
- the abrasion resistance test was carried out in accordance with JIS H 8682 and using a Suga Abrasion Tester (NUS-IS03) under the conditions of a load of 4.9 N (500 gf) (surface area of abrasion, 12 mm ⁇ 31 mm), with #1500 emery paper, and 200 back-and-forth cycles. Rating Criteria:
- the heat-treated plated substrate was FIB milled, following which the average crystal grain size and the shape of the crystals were determined from a cross-sectional SIM image (using an SMI3050SE system from SII Nanotechnologies).
- FIGS. 1 to 3 Cross-sectional SIM images of the plated substrates obtained in Example 1, Comparative Example 1 and Comparative Example 3 are shown in, respectively, FIGS. 1 to 3 .
- the plated silver layer includes silver crystals of a columnar structure. Such shapes were referred to as “columnar.”
- the silver grains in the plated silver layer are rounded. Such shapes were referred to as “round.”
- the silver crystals are horizontally elongated. Such shapes were referred to as “horizontally elongated.”
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Electroplating Methods And Accessories (AREA)
- Contacts (AREA)
- Manufacture Of Switches (AREA)
Description
- This invention relates to a silver-coated material and a method of manufacture thereof. More specifically, the invention relates to a silver-coated material suitable as a contact in connectors, switches, terminals and electronic components.
- Materials obtained by applying a copper or nickel undercoat onto a brass or phosphor-bronze surface and additionally applying on top thereof a silver plating are commonly used in the connectors and switches serving as connection components for electronic equipment. Because silver is a good conductor of electricity and heat, it is used as a plating in such connectors and switches, and also in leadframes and the like.
- It is known that, in recent years, owing to the large number of repeated switching operations carried out on the switches used in cell phones and remote controls, and to the repetition of many switching operations in a short period of time, the silver plating wears away and the contact resistance rises.
- To prevent this from happening, the approach taken to date has been to increase the thickness of the silver plating. However, with the intensifying downward pressure on the cost of electronic components year after year, product specifications which call for thinner silver plating are on the rise. Hence, there exists an urgent need to examine how to improve the abrasion resistance of silver plating.
- In general, increasing the hardness of the coating is effective for enhancing the abrasion resistance. Efforts are being made to increase the coating hardness by adding hardening agents such as antimony to the silver, but such efforts have had the opposite effect of making the coating more brittle, resulting in a deterioration of the abrasion resistance.
- In addition, Japanese Patent Publication No.
2012-49041 - The Patent Application Publication
US 2012/0301745 discloses a silver-coated material for electric contacts having a silver plating layer on a nickel underlayer, wherein crystals having a columnar structure and an average grain size of 0.5 µm are included in the plating layer. - The object of this invention is to provide a silver-coated material of excellent abrasion resistance in which, even when used as, for example, a moving contact and/or a fixed contact in a switch used over an extended period of time under conditions where switching is repeatedly carried out, the silver or silver alloy layer at the surface does not wear away and, moreover, the contact resistance does not rise.
- The inventors have conducted extensive investigations, as a result of which they have discovered that the above problem is resolved by the use of plating to form, as an outermost layer on an electrically conductive base material, a layer made of at least silver or a silver alloy, and heat-treating under specific heating conditions. This discovery led ultimately to the present invention.
- The invention is recited below.
(1) A silver-coated material having a silver coating layer on an electrically conductive base material directly and/or via an underlayer, wherein the silver coating layer is an outermost layer made of silver or a silver alloy, wherein crystals of a columnar structure having an average crystal grain size of 0.2 µm or more and 0.5 µm or less, measured in accordance with JIS H 0501, that are made of silver or a silver alloy are included in the layer made of silver or a silver alloy, and wherein the silver-coated material has a coating loss, in an abrasion resistance test, of less than 40 mg and has an initial contact resistance of less than 10 mΩ and a contact resistance of less than 10 mΩ after a sliding wear test carried out under following conditions,
Contact resistance measurement conditions:
Apparatus: Yamasaki type CRS-1 Contact Simulator
Conditions: contact load, 10 g (Au probe); sliding distance, 1 mmSliding wear test conditions: [Load] 1.6 N [Sliding range] 0.2 mm [Sliding speed] 1 mm/s [Number of cycles] 50 000,
(2) The silver-coated material according to (1) above, characterized in that the coating loss in the abrasion resistance test is less than 30 mg.
(3) A switch, characterized by using the silver-coated material according to (1) or (2) above as a moving contact and/or fixed contact for the switch.
(4) A method of manufacturing the silver-coated material according to (1) or (2) above having a silver coating layer on an electrically conductive base material directly and/or via an underlayer, wherein the silver coating layer is an outermost layer made of silver or a silver alloy, and wherein the method includes a step of forming the layer made of silver or a silver alloy by plating, and heat-treating the same at from 200 to 500°C for 1 to 299 seconds.
(5) The method of manufacturing the silver-coated material according to (4) above, characterized in that the heat treatment is carried out at from 250 to 450°C for 1 to 59 seconds.
(6) The method of manufacturing the silver-coated material according to (4) above, characterized in that the heat treatment is carried out at from 270 to 450°C for 1 to 30 seconds.
(7) The method of manufacturing the silver-coated material according to (4) above, characterized in that the heat treatment is carried out at from 300 to 450°C for 1 to 10 seconds. - According to this invention, there can be provided a silver-coated material of excellent abrasion resistance in which the silver or silver alloy layer at the surface does not wear away and, moreover, the contact resistance does not rise even when used as, for example, a moving contact and/or a fixed contact in a switch used over an extended period of time under conditions where switching is repeatedly carried out.
-
-
FIG. 1 is a cross-sectional SIM image of the silver-coated material in Example 1. -
FIG. 2 is a cross-sectional SIM image of the silver-coated material in Comparative Example 1. -
FIG. 3 is a cross-sectional SIM image of the silver-coated material in Comparative Example 3. - The silver-coated material of this invention is a silver-coated material that has, as an outermost layer on an electrically conductive base material, a layer made of at least silver or a silver alloy, and is characterized by having a coating loss in an abrasion resistance test of less than 40 mg, and having an initial contact resistance of less than 10 mΩ and a contact resistance of less than 10 mΩ after a sliding wear test carried out under the following conditions.
- Contact resistance measurement conditions:
Apparatus: Yamasaki type CRS-1 Contact Simulator
Conditions: contact load, 10 g (Au probe); sliding distance, 1 mmSliding wear test conditions: [Load] 1.6 N [Sliding range] 0.2 mm [Sliding speed] 1 mm/s [Number of cycles] 50 000, - The conductive base material is a material having, for example, electrical conductivity, spring characteristics and durability. In this invention, it is preferably made of copper or a copper alloy, or iron or an iron alloy. Copper alloys that can be preferably used include bronzes, phosphor bronzes, brasses, titanium coppers, copper-nickel-silicon (Corson) alloys and beryllium coppers. Iron alloys that can be preferably used include stainless steels (SUS) and Alloy 42.
- In the outermost layer made of silver or silver alloy, silver alloys such as Ag-Sn alloys, Ag-Cu alloys, Ag-In alloys and Ag-Se alloys have good contact characteristics and thus can be preferably used. The silver alloy is preferably one having a silver content in excess of 50% by mass.
- The outermost layer made of silver or a silver alloy is formed by plating using a known silver plating solution or silver alloy plating solution. The plating solution is not particularly limited, although a plating solution that contains cyanide as a complex is preferred. Prior to plating with a plating solution containing the cyanide as a complex, silver strike plating may be carried out. By using plating to form the outermost layer made of silver or a silver alloy, the layer can be easily and conveniently formed at a low cost.
- The outermost layer has a thickness of preferably from 0.05 to 5 µm, more preferably from 0.1 to 2 µm, and even more preferably from 0.2 to 2 µm.
- The silver-coated material of the invention may have an underlayer between the base material and the outermost layer made of silver or a silver alloy. Examples of the underlayer include a plated Ni layer, a plated copper layer and a plated cobalt layer. These may be formed with a known plating solution and under known plating conditions.
- The plating solution used to form an underlying plated Ni layer is preferably a sulfamate bath.
- The plating solution used to form an underlying plated copper layer is preferably a copper cyanide bath.
- Preferred silver-coated materials of the invention are ones having an outermost layer made of silver or a silver alloy on an electrically conductive base material, and ones having a plated copper or a plated Ni layer as an underlayer between an electrically conductive base material and an outermost layer made of silver or a silver alloy.
- The silver-coated material of the invention, after the outermost layer has been formed, is heat-treated at 200 to 500°C for 1 to 299 seconds. At a low temperature in this temperature range, it is preferable to make the treatment time longer; at a high temperature, it is preferable to make the treatment time shorter. From the standpoint of productivity, heat treatment at 250 to 450°C for 1 to 59 seconds is preferred, heat treatment at 270 to 450°C for 1 to 30 seconds is more preferred, and heat treatment at 300 to 450°C for 1 to 10 seconds is especially preferred.
- When heat treatment is carried out under this range of conditions, the spherical silver or silver alloy crystal grains in the outermost layer grow, enlarging to an average crystal grain size of 0.2 µm or more and becoming columnar in the plating thickness direction, and so the outermost layer includes crystals of a columnar structure that are made of silver or a silver alloy. As a result, the abrasion resistance of the surface was found to greatly improve. The silver-coated material of the present invention is further characterized in that the outermost layer has an average crystal grain size of 0.2 µm or more and 0.5 µm or less, and includes crystals having a columnar structure. In cases where the temperature was lower and/or the time was shorter than these conditions, the crystals did not grow and an improvement in the abrasion resistance was not observed. Conversely, in cases where the temperature was higher and/or the time was longer than these conditions, the crystals grew and an improvement in abrasion resistance was observable. However, at an average crystal grain size greater than 0.5 µm, the crystals became horizontally elongated with respect to the plating thickness direction and lamellar, and an increase in abrasion resistance as pronounced as when crystals of a column structure in the plating thickness direction are included was not observed. The shape of the crystal grains was observed from a cross-sectional SIM image in the plating thickness direction obtained after focused ion beam (FIB) milling of a plated substrate that had been heat-treated.
- Given that silver does not readily oxidize, there is no rise in contact resistance with heat treatment in this range of conditions. However, when the heat treatment temperature is higher and/or the heat treatment time is longer than these conditions, the initial contact resistance rises due to surface oxidation.
- Because the purpose of this heat treatment is to make the crystal grains of silver in the outermost layer grow and become columnar, and is not to form an oxide layer, heat treatment may be carried out in an inert gas atmosphere. However, heat treatment in open air is easy and desirable.
- The heating method for heat treatment is not particularly limited. Heat treatment may be carried out using, for example, a hot plate or a circulating hot-air oven.
- Therefore, a silver-coated material with, as the outermost layer, a layer made of silver or a silver alloy, when heat-treated in this way, has a coating loss in an abrasion resistance test of less than 40 mg and has an initial contact resistance of less than 10 mΩ and a contact resistance of less than 10 mΩ after a sliding wear test has been carried out under the following conditions.
Sliding wear test conditions: [Load] 1.6 N [Sliding range] 0.2 mm [Sliding speed] 1 mm/s [Number of cycles] 50 000 - A coating loss in the abrasion resistance test of less than 30 mg is more preferred. The coating loss can be made less than 30 mg by the heat treatment conditions.
- The abrasion resistance test was carried out in accordance with JIS H 8682 under conditions of a load of 4.9 N (500 gf) (surface area of abrasion, 12 mm × 31 mm), with #1500 emery paper, and 200 back-and-forth cycles.
- Because the silver-coated material of the invention has, as mentioned above, an excellent peel resistance and abrasion resistance, and the contact resistance does not rise, it can be suitably used in connectors and switches serving as connection components for electronic equipment. Use as a switch moving contact and/or fixed contact utilized in cell phone and remote control switches, such as tactile switches, is especially preferred. Even with long-term use under conditions where switching is repeatedly carried out, the surface silver or silver alloy layer does not wear away and the contact resistance does not rise.
- Next, this invention is described more fully based on working examples, although the invention is not limited by these examples.
- A plated substrate obtained by successively carrying out, on phosphor bronze (C5210, 25 mm × 20 mm × 0.2 mm (T)): silver strike plating to a thickness of 0.05 µm, and silver plating in a high silver cyanide bath to a thickness of 0.4 µm, was used as the test material.
- This plated substrate was heat-treated in open air using a hot plate under the Example 1 conditions in Table 1. The heat treatment temperature is the temperature of the plated substrate that has been set on a hot plate, as measured with a thermocouple.
- A plated substrate obtained by successively carrying out, on phosphor bronze (C5210, 25 mm × 20 mm × 0.2 mm (T)): copper plating to a thickness of 3 µm in a copper cyanide bath, silver strike plating to a thickness of 0.05 µm, and silver plating in a high silver cyanide bath to a thickness of 0.4 µm, was used as the test material.
- These plated substrates were heat-treated using a hot plate in open air under the Example 2 and Example 3 conditions in Table 1.
- A plated substrate obtained by successively carrying out, on phosphor bronze (C5210, 25 mm × 20 mm × 0.2 mm (T)): nickel plating to a thickness of 3 µm in a sulfamate bath, silver strike plating to a thickness of 0.05 µm, and silver plating in a high silver cyanide bath to a thickness of 0.4 µm, was used as the test material.
- This plated substrate was heat-treated using a hot plate in open air under the Example 4 conditions in Table 1.
- Aside from changing the heat treatment conditions in Example 2 to the conditions indicated in Table 1 and heating in a nitrogen atmosphere (oxygen concentration of less than 1%), a heat-treated plated substrate was obtained in the same way as in Example 2.
- Aside from changing the heat treatment conditions in Example 4 to the conditions indicated in Table 1, a heat-treated plated substrate was obtained in the same way as in Example 4.
- Aside from changing the heat treatment conditions in Example 2 to the conditions indicated in Table 1, a heat-treated plated substrate was obtained in the same way as in Example 2.
- Aside from changing the heat treatment conditions in Example 4 to the conditions indicated in Table 1, a heat-treated plated substrate was obtained in the same way as in Example 4.
- Aside from not carrying out heat treatment, a plated substrate was obtained in the same way as in Example 4.
- Aside from changing the heat treatment conditions in Example 2 to the conditions indicated in Table 1, a heat-treated plated substrate was obtained in the same way as in Example 2.
- Aside from changing the heat treatment conditions in Example 1 to the conditions indicated in Table 1, a heat-treated plated substrate was obtained in the same way as in Example 1.
- Aside from changing the heat treatment conditions in Example 4 to the conditions indicated in Table 1, heat-treated plated substrates were obtained in the same way as in Example 4.
- Abrasion resistance tests were carried out on the heat-treated plated substrates. The abrasion resistance test was carried out in accordance with JIS H 8682 and using a Suga Abrasion Tester (NUS-IS03) under the conditions of a load of 4.9 N (500 gf) (surface area of abrasion, 12 mm × 31 mm), with #1500 emery paper, and 200 back-and-forth cycles. Rating Criteria:
- Good: Coating loss in abrasion resistance test was less than 30 mg
- Fair: Coating loss in abrasion resistance test was 30 mg or more but less than 40 mg
- NG: Coating loss in abrasion resistance test was 40 or more
- The heat-treated plated substrate was FIB milled, following which the average crystal grain size and the shape of the crystals were determined from a cross-sectional SIM image (using an SMI3050SE system from SII Nanotechnologies).
- Measurement of the average crystal grain size was carried out via computation from the cross-sectional SIM image by the cutting method in accordance with JIS H 0501.
Rating Criteria: Small: average crystal grain size < 0.2 µm Medium: 0.2 µm ≤ average crystal grain size ≤ 0.5 µm Large: average crystal grain size > 0.5 µm - Cross-sectional SIM images of the plated substrates obtained in Example 1, Comparative Example 1 and Comparative Example 3 are shown in, respectively,
FIGS. 1 to 3 . - In the plated substrate of Example 1, as shown in
FIG. 1 , the plated silver layer includes silver crystals of a columnar structure. Such shapes were referred to as "columnar." In the plated substrate of Comparative Example 1, as shown inFIG. 2 , the silver grains in the plated silver layer are rounded. Such shapes were referred to as "round." In the plated substrate of Comparative Example 3, as shown inFIG. 3 , the silver crystals are horizontally elongated. Such shapes were referred to as "horizontally elongated." - The initial contact resistance and the contact resist after a sliding wear test was carried out under the following conditions were measured for the heat-treated plated substrates.
Contact resistance measurement conditions: Apparatus: Yamasaki type CRS-1 Contact Simulator Conditions: contact load, 10 g (Au probe); sliding distance, 1 mm Sliding wear test conditions: Apparatus: CRS-G2050-JNS, from Yamasaki Seiki Co. Conditions: [Load] 1.6 N [Sliding range] 0.2 mm [Sliding speed] 1 mm/s [Number of cycles] 50 000 [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Copper undercoat No Yes Yes No Yes No Yes No Ni undercoat No No No Yes No Yes No Yes Heat treatment conditions Heat treatment temperature 200°C 250°C 270°C 300°C 350°C 350°C 450°C 500°C Heat treatment time 299s 59s 30s 10s 5s 5s 1s 1s Evaluation results Abrasion resistance Fair Fair Good Good Good Good Good Good Crystal grain size medium medium medium medium medium medium medium medium Crystal shape columnar columnar columnar columnar columnar columnar columnar columnar Initial contact resistance < 10 mΩ < 10 mΩ < 10 mΩ < 10 mΩ < 10 mΩ < 10 mΩ < 10 mΩ < 10 mΩ Contact resistance after test < 10 mΩ < 10 mΩ < 10 mΩ < 10 mΩ < 10 mΩ < 10 mΩ < 10 mΩ < 10 mΩ *Heat treatment in Example 5 was carried out in a nitrogen atmosphere (oxygen concentration < 1%) [Table 2] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Copper undercoat No Yes No No No No Ni undercoat Yes No No Yes Yes Yes Heat treatment conditions Heat treatment temperature no heat treatment 150°C 250°C 300°C 350°C 550°C Heat treatment time 600s 600s 350s 320s Is Evaluation results Abrasion resistance NG NG Fair Fair Fair NG Crystal grain size small small large large large large Crystal shape round round horizontally elongated horizontally elongated horizontally elongated horizontally elongated Initial contact resistance < 10 mΩ < 10 mΩ 20 mΩ 30 mΩ 30 mΩ 20 mΩ Contact resistance after test > 100 mΩ > 100 mΩ > 100 mΩ > 100 mΩ > 100 mΩ > 100 mΩ
Claims (7)
- A silver-coated material having a silver coating layer on an electrically conductive base material directly and/or via an underlayer, wherein the silver coating layer is an outermost layer made of silver or a silver alloy, wherein crystals of a columnar structure having an average crystal grain size of 0.2 µm or more and 0.5 µm or less, measured in accordance with JIS H 0501, that are made of silver or a silver alloy are included in the layer made of silver or a silver alloy, and wherein the silver-coated material has a coating loss, in an abrasion resistance test, of less than 40 mg and has an initial contact resistance of less than 10 mΩ and a contact resistance of less than 10 mΩ after a sliding wear test carried out under following conditions.
Contact resistance measurement conditions: Apparatus: Yamasaki type CRS-1 Contact Simulator Conditions: contact load, 10 g (Au probe); sliding distance, 1 mm Sliding wear test conditions:wherein, the abrasion resistance test is carried out in accordance with JIS H 8682 under conditions of a load of 4.9 N (500 gf) (surface area of abrasion, 12 mm × 31 mm), with #1500 emery paper, and 200 back-and-forth cycles.[Load] 1.6 N[Sliding range] 0.2 mm[Sliding speed] 1 mm/s[Number of cycles] 50 000 - The silver-coated material according to claim 1, characterized in that the coating loss in the abrasion resistance test is less than 30 mg.
- A switch, characterized by using the silver-coated material according to claim 1 or 2 as a moving contact and/or fixed contact for the switch.
- A method of manufacturing the silver-coated material according to claim 1 or 2 having a silver coating layer on an electrically conductive base material directly and/or via an underlayer, wherein the silver coating layer is an outermost layer made of silver or a silver alloy, and wherein the method includes a step of forming the layer made of silver or a silver alloy by plating, and heat-treating the same at from 200 to 500°C for 1 to 299 seconds.
- The method of manufacturing the silver∼coated material according to claim 4, characterized in that the heat treatment is carried out at from 250 to 450°C for 1 to 59 seconds.
- The method of manufacturing the silver-coated material according to claim 4, characterized in that the heat treatment is carried out at from 270 to 450°C for 1 to 30 seconds.
- The method of manufacturing the silver-coated material according to claim 4, characterized in that the heat treatment is carried out at from 300 to 450°C for 1 to 10 seconds.
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JP3874621B2 (en) * | 2001-03-30 | 2007-01-31 | 株式会社神戸製鋼所 | Sn-plated copper alloy material for mating type connection terminals and mating type connection terminals |
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