EP0160761B1 - Contact électrique revêtu d'un alliage amorphe d'un métal de transition lui-même revêtu d'un film d'or - Google Patents

Contact électrique revêtu d'un alliage amorphe d'un métal de transition lui-même revêtu d'un film d'or Download PDF

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Publication number
EP0160761B1
EP0160761B1 EP84303633A EP84303633A EP0160761B1 EP 0160761 B1 EP0160761 B1 EP 0160761B1 EP 84303633 A EP84303633 A EP 84303633A EP 84303633 A EP84303633 A EP 84303633A EP 0160761 B1 EP0160761 B1 EP 0160761B1
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EP
European Patent Office
Prior art keywords
gold
electrical contact
transition metal
nickel
amorphous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP84303633A
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German (de)
English (en)
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EP0160761A1 (fr
Inventor
Rodger Lotis Gamblin
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Burlington Industries Inc
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Burlington Industries Inc
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Publication date
Application filed by Burlington Industries Inc filed Critical Burlington Industries Inc
Priority to AT84303633T priority Critical patent/ATE40721T1/de
Publication of EP0160761A1 publication Critical patent/EP0160761A1/fr
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Publication of EP0160761B1 publication Critical patent/EP0160761B1/fr
Expired legal-status Critical Current

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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
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or 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
    • 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
    • C25D5/619—Amorphous 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

Definitions

  • the invention relates to an electrical contact surface (such as an electrical switch contact) having low contact resistance, relatively low cost, acceptable solderability, and high corrosion resistance.
  • the electrical contact surface, and method of formation thereof, according to the present invention are particularly designed to replace conventional electrical contact surfaces wherein a gold layer of at least about 0.762 pm (about 30 microinches) thickness is applied over a crystalline substrate.
  • gold is currently used to insure low contact resistance, and thus effective conduction.
  • the gold is applied over a crystalline base metal such as copper, brass, or silver, with or without an intermediate strike of nickel, and the thickness of the gold layer is normally at least about 0.762 11m (about 30 microinches) (e.g. 1.27-2.54 11m (50-100 microinches).
  • the cost of the gold layer is on the order of 5 cents/cm 2.
  • gold-with such a thickness-that it is porous and thus through time the underlying material, or its corrosion products, may migrate to the surface of the gold and unacceptably raise the contact resistance. Additionally, certain organic materials or sulfur compounds can polymerize on a gold surface and cause high contact resistance. Additionally, gold has less than ideal solderability since it dissolves in and embrittles some solder alloys.
  • an electrical contact surface is provided which overcomes the drawbacks associated with the conventional electrical contact surfaces described above, in that in low and intermediate voltage and/or current signal situations effective conduction can be obtained at less cost and over longer periods of time.
  • an electrical contact having a contact resistance soon after production of less than 4 milliohms, comprising an electrically conductive substrate, an amorphous transition metal alloy deposited on said substrate, and an uncovered coating of gold over said amorphous transition metal alloy, said gold coating being between about 0.0254-0.762 11 m (1-30 microinches) thick.
  • the electrically conductive substrate is preferably a metal such as copper, bronze, brass, aluminum, or silver, and the amorphous (as opposed to crystalline) transition metal alloy is preferably electrolytically deposited thereon.
  • An "amorphous" alloy is one that has a geometric or topological configuration of the atoms forming the alloy that is different from crystalline (i.e. non-crystalline). Typically, metal alloys are crystalline. When X-ray diffraction tests are done on crystalline materials, it can be seen that the materials exhibit sharp peaks for the d-spacings between planes in the ordered crystal structure. The narrowness or width of these peaks relative to thick height gives an indication of the size of the crystals. For amorphous materials, there are no particularly sharp peaks, the amorphous material being characterized by lack of order in the atomic structure.
  • the amorphous transition metal alloy according to the invention preferably is a nickel-phosphorus alloy, such as one having about 15-25 atomic percent phosphorus (preferably about 20 percent), with cobalt, or some other transition metals, utilizable in addition to, or in place of, the nickel.
  • Various materials may be added to the plating bath to enhance the corrosion protection of the electrical contact surface being formed, particularly advantageous materials being hexafluosilicate (SiF s -), hexafluotitanate (TiF s -) or hexafluozirconate (ZrF s -) ions.
  • the amorphous nickel alloy After the amorphous nickel alloy has been electrolytically deposited on the substrate, the amorphous nickel alloy is coated with a layer of gold.
  • the contactor that results exhibits superior properties compared to conventional contactors wherein the same thickness of gold is coated on a crystalline metal alloy.
  • a gold thickness of less than 0.762 pm (30 microinches) over the amorphous nickel alloy produces an electrical contact structure according to the invention that is equal to, or superior to, conventional contactors wherein a coating of 1.27 ⁇ 2.54 ⁇ m (50-100 microinches) of gold is provided.
  • a method of producing an electrical contact surface comprising the steps of: a) immersing an electrically conductive substrate in a plating bath including transition metal alloying elements; and b) controlling the bath temperature conditions and current density at the cathode to effect electrolytic deposition of the transition metal alloying elements, in amorphous form, on the substrate; and c) applying a coating of gold having a thickness of between 0.0254-0.762 pm (1-30 microinches) to the electrolytically deposited amorphous transition metal alloy, to produce an electrical contact structure having an uncovered gold surface.
  • Nickel chloride, cobalt carbonate, and phosphorous acid are preferred bath constituents.
  • a number of bath additives can be provided to influence contact resistance and corrosion protection in a positive way.
  • Typical bath additives include boric acid, hydroxyacetic acid, acetic acid, 0-alanine, succinic acid, surfactants of the alkoxylated linear alcoholic class, SiF s - ions, TiF s - ions and ZrF s - ions.
  • the bath temperature conditions, and the current density at the cathode, are maintained so that effective electrolytic deposition takes place.
  • a deposition of an amorphous transition metal alloy can be provided on a substrate by immersing the substrate (or a portion thereof) in a plating bath.
  • Amorphous transition metal alloys have been found to have better corrosion resistance than crystalline materials, and a thinner coating of gold over an amorphous transition metal alloy produces a contactor having the same, or better, properties than a contactor formed by a thicker coating of gold over a crystalline material. Further, acceptable contacts can be obtained, according to the invention, with only a very thin coating of gold.
  • Typical transition alloys that are useful electrical contact surfaces (such as electrical switch contacts) according to the invention are nickel and cobalt.
  • Nickel is the preferred transition metal since it has the least cost of the most corrosion resistance, of suitable transition metals.
  • cobalt for all or part of the nickel, in the plating bath.
  • An amorphous deposition of the nickel on the conductive substrate (which preferably comprises a metal such as copper, bronze, brass, aluminum, or silver, or alloys thereof) is formed when phosphorous acid is included in the plating bath, and a relatively high percentage of phosphorus is provided in the alloy that is formed.
  • a phosphorus concentration of at least about 12%, and preferably of about 15-25 atomic percent is desired in order to achieve good corrosion resistance and low contact resistance.
  • the amorphous deposited alloy has about 20 atomic percent phosphorus.
  • the bath temperature conditions, and the current density at the cathode, are controlled in order to maximize the corrosion resistance and minimize the contact resistance.
  • current density is about 538.2 amp/m 2- 26909.8 amp/m 2 (about 50 amp/ft 2- 2500 amp/ft 2 ), with a range of about 1076.4 amp/m 2- 9687.6 amp/m 2 (about 100-900 amp/ft 2 ) preferred.
  • Typical temperatures are 70-85°C with 75 ⁇ 80°C preferred. Temperature is not critical, but lower temperature will have a tendency to increase the preference of cobalt for nickel in the plating where both are present in the bath.
  • Various additives may be provided in the bath in order to positively affect the contact resistance and corrosion resistance.
  • the bath contains hexafluosilicate ions at a concentration of about 0.1 molar to the solubility limit (with the addition of small amounts of HF to maintain solubility if necessary) the overall corrosion resistance of the amorphous nickel alloy may be enhanced.
  • a generally comparable enhancement of corrosion resistance may also be obtained by substituting TiF s - or ZrF s - ions for part or all of the SiFs- ions.
  • any suitable anode and cathode materials may be utilized.
  • the anode can either be inert (platinized titanium, platinum, or graphite), or can be of nickel (or like transition metal to be deposited). If TiF s -, SiF s - or ZrF a - ions are included in the bath a nickel or cobalt anode must be used. With an inert anode additions of nickel or cobalt must be made from time to time (preferably in the form of NiC0 3 or CoC0 3 ) to maintain the nickel content.
  • nickel anode With the nickel anode the content of nickel ion in the bath tends to rise since each two electrons at the anode cause the dissolution of about one nickel ion, while at the cathode both nickel and phosphorus are being reduced.
  • a nickel and an inert anode can be used together such that each carries only a portion of the current, and thus maintains a balanced bath with regard to nickel.
  • Phosphorous, in the form of phosphorous or hypophosphorous acid, and preferably in the form of phosphorous acid, must be added from time to time-irrespective of the anode construction-to maintain the proper bath balance, although the proportion of phosphorous acid is not critical and the bath balance can be maintained rather easily.
  • a coating of gold is applied over the amorphous alloy. Preferably this is accomplished by providing an electrodeposit that is applied for a controlled time at a controlled current density.
  • the thickness of the gold coating is determined by the desired end properties of the contactor produced. Within wide ranges, whatever the thickness of the gold coating on the amorphous alloy, the contactor that results can be expected to have enhanced properties compared to contactors formed by the same thickness of gold coating over a crystalline material. In fact, acceptable electric contacts can be produced even when the thickness of the gold coating is about 0.0254 pm (about 1 microinch).
  • the gold coating is in the range of 0.127-0.762 pm (5 ⁇ 30 microinches), and more preferably 0.127-0.381 pm (5-15 microinches).
  • the gold used for the coating preferably is hard gold, athough soft gold is also practical although usually with somewhat less desirable results.
  • the thickness of the amorphous transition metal alloy on the substrate is not particularly critical. It merely need be thick enough to achieve the desired results according to the invention. A preferred thickness is in the range of about 1.27-3.81 um (about 50 microinches-150 microiriches). Ranges of 0.635-25.4 ⁇ m (25 microinches-1000 microinches) are practical.
  • the electrically conductive substrate is formed into the desired final contact shape. It is then immersed in a cleaner, and the deionized water, and then a dilute hydrochloric acid solution. Then it is placed in the Ni-Co-P plating bath and after plating it is rinsed in deionized water. Then the gold plating is provided thereon in any conventional way, such as in a gold plating bath maintained at about 30-35°C with a current density of about 107.6 amp/m 2 (about 10 amp/ft 2 ). After the gold plating is applied it is again immersed in deionized water.
  • a plating bath was formed with the following composition:
  • An electrically conductive substrate was immersed in the bath, which was maintained at a temperature of about 80°C, and with a current density at the cathode of about 150 ma/cm 2 .
  • the substrate When removed from the bath, the substrate had an amorphous nickel-phosphorous alloy thereon.
  • a 0.0254 pm (one (1) microinch) strike of gold was provided on the amorphous alloy.
  • the electrical contact surface that resulted had a contact resistance that was substantially as low as a similar substrate with a 1.27 ⁇ m (50 microinch) or greater coating of gold, the contact resistance was stable over time, and as stable in corrosive environments (such as when subjected to the S0 2 test-100 percent relative humidity and 1 percent concentration of sulfur dioxide, room temperature, over forty hours-, and the mixed gas test-the same conditions as the S0 2 test only adding 1 percent nitrogen dioxide and 1 percent chlorine).
  • the electrical contact surface formed was much less expensive than the conventional one, and had better solderability characteristics.
  • the bath composition, temperature, and current density characteristics were substantially the same as in Example 1.
  • an approximately 0.254 ⁇ m (10 microinch) strike of gold was provided on the amorphous alloy.
  • the electrical contact surface that resulted had contact resistance, and other properties, equal, or superior to, an electrical contact surface formed utilizing similar materials in crystalline form, and with a 1.27 pm (50 microinch) coating of gold.
  • the bath composition for this example was as follows:
  • Example 1 The bath temperature conditions, current density, and like parameters, were substantially the same as for Example 1, and after deposition of the amorphous nickelphosphorous alloy on the substrate a 0.0254 ⁇ m (1 microinch) flash of gold was applied.
  • the electrical contact surface formed was found to have acceptable contact resistance (i.e. less than 4 milliohms when tested according to ASTM B667-80) and corrosion resistance, although it was not as good as the electrical contact surface produced in Example 1.
  • the bath composition for this Example was as follows: acid
  • the bath temperature was maintained at about 75°C, with a current density at the cathode of about 200 ma/cm 2 .
  • An analysis of the plating resulting from immersion of the substrate in this bath showed bulk values (in atomic percent) of 6.8 ⁇ 4% cobalt, 0.6 oxygen, 73.3 percent nickel, and 19.3 percent phosphorus.
  • a 0.0254 ⁇ m (1 microinch) strike of gold was provided on the amorphous alloy.
  • the electrical contact surface formed had low contact resistance and high corrosion resistance, and was an excellent substitute for conventional electrical contact surfaces of gold about 1.27 ⁇ m (about 50 microinches) thick (or thicker) applied over a crystalline base metal.
  • platings were produced on electrically conductive substrates to produce platings having about 20% phosphorous, X% cobalt, and 80-X% nickel, utilizing the constituents indicated in the following table:
  • Plating was accomplished at 75-78°C using a hard anode (e.g. platinum or platinized titanium) and a current density of about 1076.4 amp/m 2 (about 100 amp/ft 2 ).
  • a hard anode e.g. platinum or platinized titanium
  • a current density of about 1076.4 amp/m 2 (about 100 amp/ft 2 ).
  • the sum of the nickel plus cobalt is one mole/liter in each formulation, and CoCOa is the source of all the cobalt in each of the formulations. Therefore, the Co +2 /Ni +2 ratio in the bath is M/1 CoCO 3 /(-M/1 CoCO 3 ).
  • the Co/Ni ratio in the plating is %CO(80-%Co).
  • the relationship between Co +2 /Ni +2 in the bath and Co/Ni in the plate is:
  • the plating formed as actual electrical connectors, having 10% Co were coated with 0.127, 0.254 or 0.381 ⁇ m (5, 10 or 15 microinches) of hard gold, or 0.127 pm (5 microinches) soft gold, and subjected to durability cycling utilizing conventional techniques, and exposure in a BCL Class III environment, and utilizing the same material on both the PC boards and the connector openings.
  • 0.127, 0.254 or 0.381 ⁇ m 5, 10 or 15 microinches
  • 0.127 pm 5 microinches

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Composite Materials (AREA)
  • Contacts (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Manufacture Of Switches (AREA)
  • Conductive Materials (AREA)
  • Coupling Device And Connection With Printed Circuit (AREA)

Claims (9)

1. Contact électrique ayant une résistance de contact, aussitôt après sa fabrication, qui est inférieure à 4 milliohms, comprenant un substrat conducteur électriquement, un alliage d'un métal de transition amorphe déposé sur ce substrat et un placage non recouvert d'or par dessus l'alliage de métal de transition amorphe, ce placage d'or ayant une épaisseur comprise entre environ 0,0254 et 0,762 micromètre.
2. Contact électrique suivant la revendication 1 caractérisé en ce que 1 alliage de métal de transition amorphe est un alliage du type nickel phosphore.
3. Contact électrique suivant la revendication 2 caractérisé en ce que l'alliage nickel-phosphore a une teneur d'environ 15 à 25% atomique de phosphore et une teneur d'environ 5 à 15% atomique de cobalt.
4. Contact électrique suivant la revendication 3 caractérisé en ce que le placage d'or non recouvert est de l'or dur ayant une épaisseur comprise entre environ 0,127 micromètre et 0,381 micromètre.
5. Procédé de fabrication d'un contact électrique caractérisé en ce qu'il comprend les étapes consistant à; a) immerger un substrat conducteur électriquement dans un bain de placage comportant des éléments d'alliage d'un métal de transition; b) contrôler les conditions de température du bain et la densité du courant à la cathode afin d'effectuer un dépôt électrolytique das éléments d'alliages de métal de transition, sous forme amorphe, sur le substrat; et c) appliquer un placage d'or ayant une épaisseur comprise entre 0,0254 et 0,762 micromètre sur l'alliage de métal de transition amorphe déposé électrolytiquement afin de produire une structure de contact électrique ayant une surface d'or non recouverte.
6. Procédé suivant la revendication 5 caractérisé en ce que l'étape a) est réalisée en utilisant un bain de placage contenant de l'acide phosphorique et du nickel seul ou bien du nickel et du cobalt.
7. Procédé suivant la revendication 5 caractérisé en ce que l'étape b) est réalisée de telle façon que la température du bain soit comprise environ 70-85°C et que la densité de courant à la cathode soit comprise entre environ 1076,4-9687,6 Alm2 et de manière à effectuer un dépot électrolytique du matériau amorphe tel qu'il ait une épaisseur d'environ 0,635-25,4 micromètres; et en ce que l'étape (a) est réalisée en incorporant dans le bain de placage entre 0,1 molaire et à la limite de solubilité d'ions choisis dans le groupe constitué par les ions TiFs-, SiFs- et ZrFs-.
8. Procédé suivant la revendication 7 caractérisé en ce que les étapes a) et b) sont réalisées de telle façon que l'alliage amorphe déposé sur le substrat-soit un alliage du type nickel-cobalt-phosphore, ayant une teneur d'environ 15-25% atomique de phosphore et une teneur d'au moins 5% atomique de cobalt.
9. Procédé suivant la revendication 5 caractérisé en ce que l'étape c) est réalisée de manière à appliquer un placage d'or dur ayant une épaisseur comprise entre 0,127-0,381 micromètre.
EP84303633A 1984-05-11 1984-05-30 Contact électrique revêtu d'un alliage amorphe d'un métal de transition lui-même revêtu d'un film d'or Expired EP0160761B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84303633T ATE40721T1 (de) 1984-05-11 1984-05-30 Elektrischer kontakt beschichtet mit einer amorphen uebergangslegierung der selbst mit einem goldfilm beschichtet ist.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US60913784A 1984-05-11 1984-05-11
US609137 1984-05-11

Publications (2)

Publication Number Publication Date
EP0160761A1 EP0160761A1 (fr) 1985-11-13
EP0160761B1 true EP0160761B1 (fr) 1989-02-08

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EP84303633A Expired EP0160761B1 (fr) 1984-05-11 1984-05-30 Contact électrique revêtu d'un alliage amorphe d'un métal de transition lui-même revêtu d'un film d'or

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EP (1) EP0160761B1 (fr)
JP (1) JPS6129021A (fr)
AT (1) ATE40721T1 (fr)
DE (1) DE3476684D1 (fr)
ES (1) ES533300A0 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017066344A1 (fr) 2015-10-12 2017-04-20 Te Connectivity Corporation Composant électronique et procédé de production d'un composant électronique
WO2017066342A1 (fr) 2015-10-12 2017-04-20 Te Connectivity Corporation Composant électronique et procédé de production de composant électronique

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Publication number Priority date Publication date Assignee Title
DE3574075D1 (en) * 1984-08-31 1989-12-07 American Telephone & Telegraph Nickel-based electrical contact
JPH01132072A (ja) * 1987-11-18 1989-05-24 Yazaki Corp 端子、接点等の金メッキ部品
US5637925A (en) * 1988-02-05 1997-06-10 Raychem Ltd Uses of uniaxially electrically conductive articles
US4891480A (en) * 1989-02-01 1990-01-02 American Telephone And Telegraph Company, At&T Bell Laboratories Apparatus including electrical contacts
JPH0359972A (ja) 1989-07-27 1991-03-14 Yazaki Corp 電気接点
US5408574A (en) * 1989-12-01 1995-04-18 Philip Morris Incorporated Flat ceramic heater having discrete heating zones
US5468936A (en) * 1993-03-23 1995-11-21 Philip Morris Incorporated Heater having a multiple-layer ceramic substrate and method of fabrication
US6335107B1 (en) * 1999-09-23 2002-01-01 Lucent Technologies Inc. Metal article coated with multilayer surface finish for porosity reduction
FI113912B (fi) * 2001-12-13 2004-06-30 Outokumpu Oy Lisäaineellisella pinnoitteella varustettu yhdysterminaali
US7615255B2 (en) 2005-09-07 2009-11-10 Rohm And Haas Electronic Materials Llc Metal duplex method
DE102005047799A1 (de) * 2005-10-05 2007-05-24 W.C. Heraeus Gmbh Schleifringkörper zur kontinuierlichen Stromübertragung
US8652649B2 (en) * 2009-07-10 2014-02-18 Xtalic Corporation Coated articles and methods
DE102010033715A1 (de) 2010-08-07 2012-02-09 Audi Ag Ausgleichsbehälter für einen Kühlmittelkreislauf
US20130065069A1 (en) * 2011-09-09 2013-03-14 Yun Li Liu Electrodeposition of Hard Magnetic Coatings

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DE1059738B (de) * 1957-12-06 1959-06-18 Duerrwaechter E Dr Doduco Verfahren zur Herstellung eines Mehrschichtenmetalls
GB1507782A (en) * 1976-04-13 1978-04-19 Lea Ronal Inc Electrodeposition of gold
US4101389A (en) * 1976-05-20 1978-07-18 Sony Corporation Method of manufacturing amorphous alloy

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017066344A1 (fr) 2015-10-12 2017-04-20 Te Connectivity Corporation Composant électronique et procédé de production d'un composant électronique
WO2017066342A1 (fr) 2015-10-12 2017-04-20 Te Connectivity Corporation Composant électronique et procédé de production de composant électronique

Also Published As

Publication number Publication date
ES8601557A1 (es) 1985-10-16
EP0160761A1 (fr) 1985-11-13
ES533300A0 (es) 1985-10-16
JPS6129021A (ja) 1986-02-08
ATE40721T1 (de) 1989-02-15
DE3476684D1 (en) 1989-03-16

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