WO2015002838A1 - Articles revêtus comportant une couche métallique - Google Patents

Articles revêtus comportant une couche métallique Download PDF

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Publication number
WO2015002838A1
WO2015002838A1 PCT/US2014/044607 US2014044607W WO2015002838A1 WO 2015002838 A1 WO2015002838 A1 WO 2015002838A1 US 2014044607 W US2014044607 W US 2014044607W WO 2015002838 A1 WO2015002838 A1 WO 2015002838A1
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WIPO (PCT)
Prior art keywords
article
barrier layer
nickel
metal layer
layer comprises
Prior art date
Application number
PCT/US2014/044607
Other languages
English (en)
Inventor
Trevor Goodrich
John Cahalen
Alan C. Lund
Christopher A. Schuh
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Xtalic Corporation
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Filing date
Publication date
Application filed by Xtalic Corporation filed Critical Xtalic Corporation
Publication of WO2015002838A1 publication Critical patent/WO2015002838A1/fr

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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
    • 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
    • C25D5/10—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
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers
    • 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
    • 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
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • 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
    • C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12875—Platinum group metal-base component

Definitions

  • the present invention generally relates to coated articles comprising a metal layer and related methods.
  • the articles are coated using an
  • Electrodeposition is a common technique for depositing such coatings. Electrodeposition generally involves applying a voltage to a base material placed in an electrodeposition bath to reduce metal ionic species within the bath which deposit on the base material in the form of a metal, or metal alloy, coating. The voltage may be applied between an anode and a cathode using a power supply. At least one of the anode or cathode may serve as the base material to be coated. In some electrodeposition processes, the voltage may be applied as a complex waveform such as in pulse plating, alternating current plating, or reverse-pulse plating.
  • a variety of metal and metal alloy coatings may be deposited using
  • metal alloy coatings can be based on two or more transition metals including Ni, W, Fe, Co, amongst others.
  • Corrosion processes in general, can affect the structure and composition of an electroplated coating that is exposed to the corrosive environment.
  • corrosion can involve direct dissolution of atoms from the surface of the coating, a change in surface chemistry of the coating through selective dissolution or de-alloying, or a change in surface chemistry and structure of the coating through, e.g., oxidation or the formation of a passive film.
  • Some of these processes may change the topography, texture, properties, or appearance of the coating. For example, spotting and/or tarnishing of the coating may occur. Such effects may be undesirable, especially when the coating is applied at least in part to improve electrical conductivity since these effects can increase the resistance of the coating.
  • Coated articles including a layer comprising rhodium (Rh) and/or ruthenium (Ru) and related methods are provided.
  • an article comprises a base material, a barrier layer formed on the base material, a metal layer formed on the barrier layer, and a layer comprising Rh and/or Ru formed on the metal layer and having a thickness between about 1 microinch and about 5 microinches.
  • a method comprises electrodepositing a barrier layer on a base material; electrodepositing a metal layer on the barrier layer; and electrodepositing a layer comprising Rh and/or Ru and having a thickness between about 1 microinch and about 5 microinches on the metal layer.
  • FIG. 1 shows a coated article, according to some embodiments.
  • Coated articles including a layer comprising Rh and/or Ru also referred to herein as a "Rh and/or Ru layer" and methods for applying coatings are described.
  • the article may include a base material and a multi-layer coating formed thereon.
  • the coating includes a base material, a barrier layer formed on the base material, a metal layer formed on the barrier material, and a Rh and/or Ru layer formed on the metal layer.
  • the barrier layer comprises an alloy (e.g., nickel alloy, silver alloy) and the metal layer comprises a precious metal (e.g., Ru, Rh, Os, Ir, Pd, Pt, Ag, and/or Au).
  • the coating may be applied using an electrodeposition process.
  • the coating can exhibit desirable properties and characteristics such as durability, corrosion resistance, and high conductivity, which may be beneficial, for example, in electrical applications.
  • FIG. 1 shows an article 10 according to a non-limiting embodiment.
  • the article has coating 20 formed on a base material 30.
  • the coating may comprise barrier layer 40 formed on the base material, metal layer 50 formed on the barrier layer, and Rh and/or Ru layer 60 formed on the metal layer.
  • Each layer may be applied using a suitable process, as described in more detail below. It should be understood that the coating may include more than three layers. However, in some embodiments, the coating may only include three layers, as shown.
  • the inventors have discovered that formation of a Rh and/or Ru layer on a metal layer results in articles with desired properties as compared to articles formed comprising only the metal layer. For example, the presence of a metal layer and a Rh and/or Ru layer on an article as compared to only a metal layer leads to improved coloration (e.g., desired shade/tone, color stability over time, etc.), improved durability, and/or improved corrosion resistance.
  • improved coloration e.g., desired shade/tone, color stability over time, etc.
  • layer 60 comprises Rh and does not comprise (i.e., is free of) Ru.
  • the layer may comprise Rh in the form of an alloy (e.g., with one or more additional metals), or in the form of a non-alloyed (substantially pure) Rh metal.
  • layer 60 comprises Ru and does not comprise (i.e., is free of) Rh.
  • the layer may comprise Ru in the form of an alloy, or in the form of a non-alloyed (substantially pure) Ru metal.
  • layer 60 comprises Rh and Ru in the form of an alloy.
  • the Rh and/or Ru layer has a thickness greater than about 1 microinch. In some cases, the Rh and/or Ru layer has a thickness between about 1 microinch and about 5 microinches.
  • the inventors have discovered that coated articles comprising a Rh and/or Ru layer having a thickness less than about 1 microinch or greater than about 5 microinches can result in inferior performance.
  • Rh and/or Ru layers having a thickness less than 1 microinch may provide incomplete coverage of the metal layer which can affect the overall coating appearance (e.g., may affect the color stability overtime), wear performance, and/or corrosion resistance.
  • Rh and/or Ru layers having a thickness greater than 5 microinches can have highly stressed and/or cracked deposits which can affect the coating appearance and/or wear performance.
  • the barrier layer comprises one or more metals.
  • the barrier layer is generally comprised of a layer that is conductive.
  • the barrier layer comprises a material that has some corrosion resistance to the conditions under which the article is to be employed.
  • the barrier layer acts as a diffusion barrier between the base material and subsequent layers of material.
  • the barrier layer comprises nickel or consists essentially of nickel.
  • the barrier layer comprises silver or consists essentially of silver.
  • the barrier layer comprises palladium or consists essentially of palladium.
  • the barrier layer comprises a metal alloy. In some cases, alloys that comprise nickel (e.g., nickel-tungsten alloys) or silver (e.g., silver, tungsten, and/or molybdenum) are preferred.
  • the barrier layer comprises a nickel alloy (i.e., nickel- based alloys).
  • Nickel alloys are known in the art. For example, see U.S. Publication No. 2011/0008646 by Cahalen et al., filed July 10, 2009, and U.S. Publication No.
  • the nickel-alloy further comprises tungsten and/or
  • molybdenum e.g., a nickel-tungsten alloy, a nickel-molybdenum alloy, a nickel- tungsten-molybdenum alloy.
  • nickel alloys may also be employed.
  • the nickel alloy may further comprise cobalt, phosphorus, and/or palladium.
  • the weight percent of nickel in the alloy may be between 25-75 weight percent; and, in some cases, between 50 and 70 weight percent. In these cases, the remainder of the alloy may be tungsten and/or molybdenum. Other weight percentages outside of this range may be used as well.
  • the weight percent of tungsten in the alloy may be greater than or equal to 10 weight percent; in some cases, greater than or equal to 14 weight percent; in some cases, greater than or equal to 15 weight percent; and, in some cases greater than or equal to 20 weight percent.
  • the total weight percentage of tungsten in the alloy is less than or equal to 35 weight percent; in some cases, the total weight percentage of tungsten in the alloy is less than or equal to 30 weight percent; in some cases, the total weight percentage of tungsten in the alloy is less than or equal to 28 weight percent; and, the total weight percentage of tungsten in the alloy is less than or equal to 25 weight percent.
  • the barrier layer comprises a silver alloy (i.e., silver-based alloys). Such alloys may also comprise tungsten and/or molybdenum. Silver alloys are known in the art, for example, see U.S. Publication No. 2011/0223442 by Dadvand et al., filed March 12, 2010, herein incorporated by reference.
  • the barrier layer comprises a silver- tungsten alloy. Other silver alloys may also be employed.
  • the atomic percent of tungsten and/or molybdenum in the alloy may be between 0.1 atomic percent and 50 atomic percent; and, in some cases, between 0.1 atomic percent and 20 atomic percent, the remainder being silver.
  • the atomic percent of tungsten and/or molybdenum in the alloy may be at least 0.1 atomic percent, at least 1 atomic percent, at least 1.5 atomic percent, at least 5 atomic percent, at least 10 atomic percent, or at least 20 atomic percent, the remainder being silver. Other atomic percentages outside of this range may be used as well.
  • the barrier layer may have a thickness suitable for a particular application.
  • the barrier layer thickness may be greater than about 1 microinch (e.g., between about 1 microinch and about 250 microinches, between about 1 microinch and about 200 microinches, between about 1 microinch and about 150 microinches, between about 1 microinch and about 100 microinches, between about 1 microinch and 50 microinches); in some cases, greater than about 5 microinches (e.g., between about 5 microinches and about 100 microinches, between about 5 microinches and 50 microinches); greater than about 25 microinches (e.g., between about 25 microinches and about 100 microinches, between about 1 microinch and 50 microinches). It should be understood that other barrier layer thicknesses may also be suitable. Thickness may be measured by techniques known to those in the art.
  • the barrier layer may be formed directly on the base material. Such embodiments may be preferred over certain prior art constructions that utilize a layer between the barrier layer and the base material because the absence of such an intervening layer can save on overall material costs. Though, it should be understood that in other embodiments, one or more layers may be formed between the barrier layer and the base material.
  • the metal layer may comprise one or more precious metals.
  • suitable precious metals include Ru, Rh, Os, Ir, Pd, Pt, Ag, and/or Au.
  • the precious metal is selected from the group consisting Ru, Os, Ir, Pd, Pt, Ag, and Au, or combinations thereof. Gold may be preferred in some embodiments.
  • the metal layer consists essentially of one precious metal. In some embodiments, it may be preferable that the metal layer is free of tin. In some cases, the precious metal is not rhodium and/or is not ruthenium. In other cases, the metal layer may comprise an alloy that includes at least one precious metal and at least one other metal. The other metal may be selected from Ni, W, Fe, B, S, Co, Mo, Cu, Cr, Zn, and Sn, amongst others.
  • the metal layer comprises a silver alloy (i.e., silver-based alloys). Such alloys may also comprise tungsten and/or molybdenum. Silver alloys are known in the art, for example, see U.S. Publication No. 2011/0223442 by Dadvand et al., filed March 12, 2010, herein incorporated by reference.
  • the barrier layer comprises a silver- tungsten alloy. Other silver alloys may also be employed. In some cases, the atomic percent of tungsten and/or molybdenum in the alloy may be between 0.1 atomic percent and 50 atomic percent; and, in some cases, between 0.1 atomic percent and 20 atomic percent, the remainder being silver.
  • the atomic percent of tungsten and/or molybdenum in the alloy may be at least 0.1 atomic percent, at least 1 atomic percent, at least 1.5 atomic percent, at least 5 atomic percent, at least 10 atomic percent, or at least 20 atomic percent, the remainder being silver. Other atomic percentages outside of this range may be used as well.
  • the metal layer comprises a silver-based alloy and the barrier layer comprises a nickel-based alloy. In some cases, the metal layer comprises a silver-based alloy further comprising molybdenum and/or tungsten and the barrier layer comprises a nickel-based alloy further comprising molybdenum and/or tungsten. In some cases, the metal layer comprises a silver-tungsten alloy and the barrier layer comprises a nickel-tungsten alloy.
  • the metal layer may have any suitable thickness. It may be advantageous for the metal layer to be thin, for example, to save on material costs.
  • the metal layer thickness may be less than 30 microinches (e.g., between about 1 microinch and about 30 microinches; in some cases, between about 5 microinches and about 30 microinches); in some cases the metal layer thickness may be less than 20 microinches (e.g., between about 1 microinch and about 20 microinches; in some cases, between about 5 microinches and about 20 microinches); and, in some cases, the metal layer thickness may be less than 10 microinches (e.g., between about 1 microinch and about 10 microinches; in some cases, between about 5 microinches and about 10 microinches). It should be understood that other metal layer thicknesses may also be suitable.
  • the metal layer may be formed directly on the barrier material. Such embodiments may be preferred over certain prior art constructions that utilize a layer between the metal layer and the barrier material because the absence of such an intervening layer can save on overall material costs. Though, it should be understood that in other embodiments, one or more layers may be formed between the metal layer and the barrier material.
  • the metal layer may cover the entire barrier layer. However, it should be understood that in other embodiments, the metal layer covers only part of the barrier layer. In some cases, the metal layer covers at least 50% of the surface area of the barrier layer; in other cases, at least 75% of the surface area of the barrier layer. In some cases, an element from the barrier layer may be incorporated within the metal layer and/or an element from the metal layer may be incorporated into the barrier layer.
  • the coating may have a particular micro structure.
  • at least a portion of the coating may have a nanocrystalline micro structure.
  • a “nanocrystalline” structure refers to a structure in which the number- average size of crystalline grains is less than one micron.
  • the number- average size of the crystalline grains provides equal statistical weight to each grain and is calculated as the sum of all spherical equivalent grain diameters divided by the total number of grains in a representative volume of the body.
  • the number- average size of crystalline grains may, in some embodiments, be less than 100 nm (e.g., 1 nm to 100 nm).
  • At least a portion of the coating may have an amorphous structure.
  • an amorphous structure is a non-crystalline structure characterized by having no long range symmetry in the atomic positions. Examples of amorphous structures include glass, or glass-like structures.
  • Some embodiments may provide coatings having a nanocrystalline structure throughout essentially the entire coating. Some embodiments may provide coatings having an amorphous structure throughout essentially the entire coating.
  • the coating may comprise various portions having different microstructures.
  • the barrier layer may have a different micro structure than the metal layer and/or the Rh and/or Ru layer.
  • the coating may include, for example, one or more portions having a nanocrystalline structure and one or more portions having an amorphous structure.
  • the coating comprises nanocrystalline grains and other portions which exhibit an amorphous structure.
  • the coating, or a portion thereof i.e., a portion of the barrier layer, a portion of the metal layer, a portion of the Rh and/or Ru layer, or a portion of two of the layers, or all three of the layers
  • the coating may comprise a portion having crystal grains, a majority of which have a grain size greater than one micron in diameter.
  • the coating may include other structures or phases, alone or in combination with a nanocrystalline portion or an amorphous portion. Those of ordinary skill in the art would be able to select other structures or phases suitable for use in the context of the invention.
  • the coating i.e., the barrier layer, the metal layer, the Rh and/or Ru layer, or two of the layers, or all three of the layers
  • the coating may be substantially free of elements or compounds having a high toxicity or other disadvantages.
  • the coating is free of chromium (e.g., chromium oxide), which is often deposited using chromium ionic species that are toxic (e.g., Cr 6+ ).
  • Such coating may provide various processing, health, and environmental advantages over certain previous coatings.
  • metal, non-metal, and/or metalloid materials, salts, etc. may be incorporated into the coating.
  • metal, non-metal, and/or metalloid materials, salts, etc. e.g., phosphate or a redox mediator such as potassium ferricyanide, or fragment thereof
  • phosphate or a redox mediator such as potassium ferricyanide, or fragment thereof
  • composition of the coatings, or portions or layers thereof may be any suitable composition of the coatings, or portions or layers thereof.
  • AES Auger electron spectroscopy
  • XPS X-ray photoelectron spectroscopy
  • AES and/or XPS may be used to characterize the chemical composition of the surface of the coating.
  • Base material 30 may be coated to form coated articles, as described above.
  • the base material may comprise an electrically conductive material, such as a metal, metal alloy, intermetallic material, or the like.
  • Suitable base materials include steel, copper, aluminum, brass, bronze, nickel, polymers with conductive surfaces and/or surface treatments, transparent conductive oxides, amongst others.
  • copper base materials are preferred.
  • a lubricant layer may be formed as an upper portion of the coating.
  • the lubricant layer may comprise, for example, an organic material, a self- assembled monolayer, carbon nanotubes, and the like. In some cases, the presence of a lubricant layer reduces the coefficient of friction of the coating as compared to a substantially similar coating but which does not include the lubricant layer.
  • the lubricant layer may be formed of any suitable material, for example halogen-containing organic lubricant, a polyphenyl-containing organic lubricant, or a polyether-containing lubricant. In one embodiment, the lubricant layer is formed of a halogen-containing organic lubricant. Specific non-limiting examples of lubricants include EvabriteTM (Enthone), Au lube (AMP), NyeTact® 570H (Nye Lubricants), FS-5 (Gabriel
  • a lubricant is chlorotrifluoroethylene.
  • the lubricant layer comprises a monolayer formed on the surface of the coating.
  • the lubricant may be as described in U.S. Publication No.
  • an article comprising the coating may exposed (e.g., dipped into) to the lubricant (e.g., optionally in a solution), and the article may then be allowed to dry, thereby forming the lubricant layer on the upper portion of the coating.
  • the lubricant e.g., optionally in a solution
  • an article comprising a lubricant layer formed on coating may have a reduced coefficient of friction as compared to a substantially similar article which does not comprise the lubricant layer.
  • the article having the lubricant layer has a co-efficient of friction which is at least two times less, at least three times less, at least four times less, at least five times less, or at least ten times less than an article which not having the lubricant layer.
  • an article having a lubricant layer may have better wear durability as compared to a substantially similar article which does not have a lubricant layer.
  • suitable methods to determine the wear durability of a material e.g., ball-on-plate-type reciprocating friction abrasion test, wherein the ball and plate both are coated with a layer of the alloy, and optionally the lubricant layer).
  • minimal or no wear- through may be observed for an article comprising a silver-based alloy and a lubricant layer over 50 cycles, 100 cycles, 250 cycles, 500 cycles, or 1000 cycles, with a 100 g applied load, wherein a substantially similar article which does not comprise the lubricant layer may show substantial or complete wear- through.
  • the articles can be used in a variety of applications including electrical applications such as electrical connectors (e.g., plug-type).
  • the coating can impart desirable characteristics to an article, such as durability, corrosion resistance, and improved electrical conductivity. These properties can be particularly advantageous for articles in electrical applications such as electrical connectors, which may experience rubbing or abrasive stress upon connection to and/or disconnection from an electrical circuit that can damage or otherwise reduce the conductivity of a conductive layer on the article.
  • Non-limiting examples of electrical connectors include infrared connectors, USB connectors, battery chargers, battery contacts, automotive electrical connectors, etc.
  • the presence of the first layer of a coating may provide at least some of the durability and corrosion resistance properties to the coating.
  • the coating may impart decorative qualities.
  • the coatings described herein may impart advantageous properties to an article, such as an electrical connector.
  • the coating, or layer of the coating may have a low electrical resistivity.
  • the electrical resistivity may be less than 100 microohm-centimeters, less than 50 microohm-centimeters, less than 10 microohm-centimeters, or less than 2 microohm-centimeters.
  • the coating or layer of the coating may have a hardness of at least 1 GPa, at least
  • Coating 20 may be formed using an electrodeposition process.
  • Electrodeposition generally involves the deposition of a material (e.g., electroplate) on a substrate by contacting the substrate with an electrodeposition bath and flowing electrical current between two electrodes through the electrodeposition bath, i.e., due to a difference in electrical potential between the two electrodes.
  • a material e.g., electroplate
  • methods described herein may involve providing an anode, a cathode, an electrodeposition bath (also known as an electrodeposition fluid) associated with (e.g., in contact with) the anode and cathode, and a power supply connected to the anode and cathode.
  • the power supply may be driven to generate a waveform for producing a coating, as described more fully below.
  • the barrier layer, the metal layer, and the Rh and/or Ru layer of the coating may be applied using separate electrodeposition baths.
  • individual articles may be connected such that they can be sequentially exposed to separate electrodeposition baths, for example in a reel-to-reel process.
  • articles may be connected to a common conductive substrate (e.g., a strip).
  • each of the electrodeposition baths may be associated with separate anodes and the interconnected individual articles may be commonly connected to a cathode.
  • the electrodeposition process(es) may be modulated by varying the potential that is applied between the electrodes (e.g., potential control or voltage control), or by varying the current or current density that is allowed to flow (e.g., current or current density control).
  • the coating may be formed (e.g.,
  • electrodeposited using direct current (DC) plating, pulsed current plating, reverse pulse current plating, or combinations thereof.
  • DC direct current
  • pulsed current plating pulsed current plating
  • reverse pulse current plating may be preferred, for example, to form the barrier layer (e.g., nickel-tungsten alloy).
  • Pulses, oscillations, and/or other variations in voltage, potential, current, and/or current density may also be incorporated during the electrodeposition process, as described more fully below.
  • pulses of controlled voltage may be alternated with pulses of controlled current or current density.
  • an electrical potential may exist on the substrate (e.g., base material) to be coated, and changes in applied voltage, current, or current density may result in changes to the electrical potential on the substrate.
  • the electrodeposition process may include the use waveforms comprising one or more segments, wherein each segment involves a particular set of electrodeposition conditions (e.g., current density, current duration, electrodeposition bath temperature, etc.), as described more fully below.
  • Some embodiments of the invention involve electrodeposition methods wherein the grain size of electrodeposited materials (e.g., metals, alloys, and the like) may be controlled.
  • selection of a particular coating (e.g., electroplate) composition such as the composition of an alloy deposit, may provide a coating having a desired grain size.
  • electrodeposition methods e.g.,
  • electrodeposition conditions described herein may be selected to produce a particular composition, thereby controlling the grain size of the deposited material.
  • the methods of the invention may utilize certain aspects of methods described in U.S. Patent
  • a nickel-based alloy and/or metal coating may be electrodeposited according to the methods described in U.S. Publication No. 2011/0008646 by Cahalen et al., filed July 10, 2009, and/or U.S. Publication No. 2012/0328904 by Baskin et al., filed June 22, 2012, each herein incorporated by reference.
  • a silver-based alloy and/or metal coating may be electrodeposited according to the methods described in U.S. Publication No.
  • a coating, or portion thereof may be electrodeposited using direct current (DC) plating.
  • a substrate e.g., electrode
  • an electrodeposition bath comprising one or more species to be deposited on the substrate.
  • a constant, steady electrical current may be passed through the electrodeposition bath to produce a coating, or portion thereof, on the substrate.
  • the potential that is applied between the electrodes e.g., potential control or voltage control
  • the current or current density that is allowed to flow e.g., current or current density control
  • pulses, oscillations, and/or other variations in voltage, potential, current, and/or current density may be incorporated during the electrodeposition process.
  • pulses of controlled voltage may be alternated with pulses of controlled current or current density.
  • the coating may be formed (e.g., electrodeposited) using pulsed current electrodeposition, reverse pulse current electrodeposition, or combinations thereof.
  • a bipolar waveform may be used, comprising at least one forward pulse and at least one reverse pulse, i.e., a "reverse pulse sequence.”
  • the electrodeposition baths described herein are particularly well suited for depositing coatings using complex waveforms such as reverse pulse sequences.
  • the at least one reverse pulse immediately follows the at least one forward pulse.
  • the at least one forward pulse immediately follows the at least one reverse pulse.
  • the bipolar waveform includes multiple forward pulses and reverse pulses. Some embodiments may include a bipolar waveform comprising multiple forward pulses and reverse pulses, each pulse having a specific current density and duration.
  • the use of a reverse pulse sequence may allow for modulation of composition and/or grain size of the coating that is produced.
  • a coating may be applied using an electrodeposition process at a current density of at least 0.001 A/cm 2 , at least 0.01 A/cm 2 , or at least 0.02 A/cm 2 . Current densities outside these ranges may be used as well. In some cases, a direct current is employed having a direct current density of greater than about 10 mA/cm , greater than about 15 mA/cm 2 , greater than about 20 mA/cm 2 , greater than about 30 mA/cm 2 , or greater than about 50 mA/cm .
  • the frequency may be any suitable frequency (e.g., between 0.1 Hertz and about 100 Hz).
  • the voltage may be any suitable voltage (e.g., between about 0.1 V and about 1 V).
  • the deposition rate of the coating may be controlled. In some instances, the deposition rate may be at least 0.1 microns/minute, at least 0.3 microns/minute, at least 1 micron/minute, or at least 3 microns/minute. Deposition rates outside these ranges may be used as well.
  • the electrodeposition processes described herein are distinguishable from electroless processes which primarily, or entirely, use chemical reducing agents to deposit the coating, rather than an applied voltage.
  • the electrodeposition baths described herein may be substantially free of chemical reducing agents that would deposit coatings, for example, in the absence of an applied voltage.
  • the electrodeposition processes use suitable electrodeposition baths. Such baths typically include species that may be deposited on a substrate (e.g., electrode) upon application of a current.
  • an electrodeposition bath comprising one or more metal species (e.g., metals, salts, other metal sources) may be used in the
  • the electrochemical bath comprises nickel species (e.g., nickel sulfate) and tungsten species (e.g., sodium tungstate) and may be useful in the formation of, for example, nickel- tungsten alloy coatings.
  • nickel species e.g., nickel sulfate
  • tungsten species e.g., sodium tungstate
  • the electrodeposition baths comprise an aqueous fluid carrier (e.g., water).
  • aqueous fluid carrier e.g., water
  • other fluid carriers including, but not limited to, molten salts, cryogenic solvents, alcohol baths, and the like.
  • the pH of the electrodeposition bath can be from about 2.0 to 12.0.
  • the electrodeposition bath may be selected to have a pH from about 7.0-9.0.
  • the electrodeposition bath may have a pH from about 7.6 to 8.4, or, in some cases, from about 7.9 to 8.1.
  • the pH may be outside the above-noted ranges.
  • the pH of the bath may be adjusted using any suitable agent known to those of ordinary skill in the art.
  • the pH of the bath is adjusted using a base, such as a hydroxide salt (e.g., potassium hydroxide).
  • the pH of the bath is adjusted using an acid (e.g., nitric acid).
  • the electrodeposition baths may include other additives, such as wetting agents, complexing agents, brightening or leveling agents, and the like. Those of ordinary skill in the art would be able to select appropriate additives for use in a particular application.
  • the electrodeposition bath may comprise at least one complexing agent (i.e., a complexing agent or mixture of complexing agents).
  • a complexing agent refers to any species which can coordinate with the ions contained in the solution.
  • a complexing agent or mixture of complexing agents may permit codeposition of at least two elements.
  • the baths may include at least one wetting agent.
  • a wetting agent refers to any species capable of reducing the surface tension of the electrodeposition bath and/or increasing the ability of gas bubbles to detach from surfaces in the bath.
  • the substrate may comprise a hydrophilic surface, and the wetting agent may enhance the compatibility (e.g., wettability) of the bath relative to the substrate.
  • the wetting agent may also reduce the number of defects within the metal coating that is produced.
  • the wetting agent may comprise an organic species, an inorganic species, an organometallic species, or combinations thereof.
  • the wetting agent may be selected to exhibit compatibility (e.g., solubility) with the electrodeposition bath and components thereof.
  • the baths may include at least one brightening agent.
  • the brightening agent may be any species that, when included in the baths described herein, improves the brightness and/or smoothness of the electrodeposited coating produced.
  • the brightening agent is a neutral species.
  • the brightening agent comprises a charged species (e.g., a positively charged ion, a negatively charged ion).
  • ionic species wetting agent, complexing agent and/or other additives (e.g., brightening agents) suitable for use in a particular application.
  • the additives in a bath are compatible with electrodeposition processes, i.e., a bath may be suitable for electrodeposition processes.
  • a bath may be suitable for electrodeposition processes.
  • One of ordinary skill in the art would be able to recognize a bath that is suitable for electrodeposition processes Likewise, one of ordinary skill in the art would be able to recognize additives that, when added to a bath, would make the bath not suitable for electrodeposition processes.
  • the operating range for the electrodeposition baths described herein is 5-100°C, 10-70°C, 10-30°C, 25-80°C, or, in some cases, 40-70°C. In some cases, the temperature is less than 80°C. However, it should be understood that other temperature ranges may also be suitable.
  • Methods of the invention may be advantageous in that coatings having various compositions may be readily produced by a single electrodeposition step.
  • a coating comprising a layered composition, graded composition, etc. may be produced in a single electrodeposition bath and in a single deposition step by selecting a waveform having the appropriate segments.
  • the coated articles may exhibit enhanced corrosion resistance and surface properties.
  • the invention provides coated articles that are capable of resisting corrosion, and/or protecting an underlying substrate material from corrosion, in one or more potential corrosive environments.
  • corrosive environments include, but are not limited to, aqueous solutions, acid solutions, alkaline or basic solutions, or combinations thereof.
  • coated articles described herein may be resistant to corrosion upon exposure to (e.g., contact with, immersion within, etc.) a corrosive environment, such as a corrosive liquid, vapor, or humid environment.
  • the corrosion resistance of coated articles may be assessed using tests such as
  • the temperature and relative humidity may also be controlled. For example, the temperature may be 30 +/- 1 °C, and the relative humidity may be 70 +/- 2%.
  • the exposure time of an article to a gas or gas mixture can be variable, and is generally specified by the end user of the product or coating being tested.
  • the exposure time may be at least 30 minutes, at least 2 hours, at least 1 day, at least 5 days, or at least 40 days.
  • the sample is examined (e.g., visually by human eye and/or instrumentally as described below) for signs of change to the surface appearance and/or electrical conductivity resulting from corrosion and/or spotting.
  • the test results can be reported using a simple pass/fail approach after the exposure time.
  • the coating subjected to the test conditions discussed above may be evaluated, for example, by measuring the change in the appearance of the coating. For instance, a critical surface area fraction may be specified, along with a specified time. If, after testing for the specified time, the fraction of the surface area of the coating that changes in appearance resulting from corrosion is below the specified critical value, the result is considered passing. If more than the critical fraction of surface area has changed in appearance resulting from corrosion, then the result is considered failing.
  • the extent of corrosive spotting may be determined. The extent of spotting may be quantified by determining the number density and/or area density of spots after a specified time. For example, the number density may be determined counting the number of spots per unit area (e.g., spots/cm ).
  • the spot area density can be evaluated by measuring the fraction of the surface area occupied by the spots, where, for example, an area density equal to unity indicates that 100% of the surface area is spotted, an area density equal to 0.5 indicates that 50% of the surface area is spotted, and an area density equal to 0 indicates that none of the surface area is spotted.
  • the coated article that is exposed to a mixed flowing gas according to ASTM B845, protocol Class Ila, for 5 days has a spotting area density of less than 0.10; in some cases, less than 0.05; and, in some cases, 0.
  • the coated article exposed to these conditions has a number density of spots of less than 3 spots/cm 2 ; in some embodiments, less than 2 spots/cm 2 ; and, in some embodiments, 0 spots/cm . It should be understood that spotting area densities and the number density of spots may be outside the above-noted ranges.
  • the low-level contact resistance of a sample may be determined before and/or after exposure to a corrosive environment for a set period of time according to one of the tests described above.
  • the low-level contact resistance may be determined according to specification EIA 364, test procedure 23.
  • the contact resistivity of a sample may be measured by contacting the sample under a specified load and current with a measurement probe having a defined cross-sectional area of contact with the sample.
  • the low-level contact resistance may be measured under a load of 25 g, 50g, 150 g, 200 g, etc.
  • the low-level contact resistance decreases as the load increases.
  • a threshold low-level contact resistance value may be set where measurement of a low-level contact resistance value for a sample above the threshold indicates that the sample failed the test.
  • the threshold low-level contact resistance value under a load of 25 g after 5 days exposure to mixed flowing gas according to ASTM B845, protocol Class Ila may be greater than 1 mOhm, greater than 10 mOhm, greater than 100 mOhm, or greater than 1000 mOhm. It should be understood that other threshold low-level contact resistance values may be achieved.
  • a coated article has reduced low-level contact resistance. Reduced low-level contact resistance may be useful for articles used in electrical applications such as electrical connectors.
  • an article may have a low-level contact resistance under a load of 25 g of less than about 100 mOhm; in some cases, less than about 10 mOhm; in some cases, less than about 5 mOhm; and, in some cases, less than about 1 mOhm. It should be understood that the article may have a low-level contact resistance outside this range as well. It should also be understood that the cross- sectional area of contact by the measurement probe may affect the value of the measured low-level contact resistance.
  • Durability of the coated articles may also be tested.
  • durability tests may be performed in conjunction with the corrosion tests discussed above and/or contact resistance measurements.
  • a durability test may comprise rubbing the surface of a coated article with an object for a period of time and then visually inspecting the coating for damage and/or measuring the contact resistance of the coating.
  • a counterbody may be held against the surface of a coated article at a set load and the coated article may be reciprocated such that the counterbody rubs against the surface of the coated article.
  • the counterbody may be held against the surface of a coated article at a load of 50 g.
  • the duration of the reciprocal motion may be measured, for example, by the number of cycles per unit time per unit time.
  • the reciprocal motion may be carried out for 500 seconds at a rate of 1 cycle per second.
  • durability may be measured before and/or after subjection of an article to a corrosion test as discussed in more detail above.
  • the contact resistance of the coating may be measured as described above.
  • the coating may be visually inspected for wear tracks.
  • the wear tracks may, in some embodiments, be analyzed by measuring the width of exposed base material between the wear tracks after a specific number of cycles under a specific load. In some instances, the analysis may be a "pass/fail" test, where a threshold width of exposed base material between wear tracks is set such that the presence of a width of exposed base material above the threshold indicates the article failed the test.
  • Nanocrystalline NiW alloy deposits in the following examples were produced using a pulsed waveform and suitable bath chemistry operating at 60 °C.
  • Nickel deposits in the following examples were produced using a DC current and nickel sulfamate plating chemistry operating at 60 °C and pH 3.8.
  • the bath comprised Ni sulfamate at 431-533 g/L, NiCl 2 -6H 2 0 at 14-21 g/L, and boric acid at 40-50 g/L.
  • Nanocrystalline AgW alloy deposits in the following examples were produced using a DC current and suitable bath chemistry operating at 50 °C.
  • Rhodium deposits in the following examples were produced using a DC current and rhodium sulfate plating chemistry at 50 °C and pH 2.0.
  • the bath comprised rhodium sulfate at 10 g/L rhodium metal and an organic brightening agent.
  • MFG class IIA testing refers to Mixed Flowing Gas test environment class IIA (ASTM B845).
  • Heat and humidity testing refers to a heat and humidity test conducted in an environmental chamber which maintains the temperature at 85 °C and the relative humidity at 85% RH using distilled water.
  • Dry heat testing refers to a dry heat test conducted in a constant temperature oven maintained at 150 °C for 1000 hours.
  • Neutral salt spray testing refers to a neutral salt spray test conducted in an environmental chamber with a 5% sodium chloride salt fog per the ASTM B-l 17 standard test procedure.
  • a series of flat coupons were cleaned, activated, and subsequently plated with 40 microinches of a nanocrystalline NiW alloy, and 80 microinches of a nanocrystalline AgW alloy.
  • the set of coupons was subjected to each of the tests shown in Table 2. The results on these tests showed some level of discoloration or corrosion in all cases.
  • Example 3 A series of flat coupons were cleaned, activated, and subsequently plated with 40 microinches of a nanocrystalline NiW alloy, 80 microinches of a nanocrystalline AgW alloy, and 0.5 microinches of rhodium. The set of coupons was subjected to each of the tests shown in Table 2. The results on these tests showed some level of discoloration or corrosion distributed across the coupons in all cases.
  • Example 3 A series of flat coupons were cleaned, activated, and subsequently plated with 40 microinches of a nanocrystalline NiW alloy, 80 microinches of a nanocrystalline AgW alloy, and 0.5 microinches of rhodium. The set of coupons was subjected to each of the tests shown in Table 2. The results on these tests showed some level of discoloration or corrosion distributed across the coupons in all cases. Example 3
  • a series of flat coupons were cleaned, activated, and subsequently plated with 40 microinches of a nanocrystalline NiW alloy, 80 microinches of a nanocrystalline AgW alloy, and 1.5 microinches of rhodium.
  • the set of coupons was subjected to each of the tests shown in Table 2. The result on the MFG test showed slight discoloration distributed across the coupons. The other test conditions showed no evidence of discoloration or corrosion.
  • Example 5 A series of flat coupons were cleaned, activated, and subsequently plated with 40 microinches of a nanocrystalline NiW alloy, 80 microinches of a nanocrystalline AgW alloy, and 3 microinches of rhodium. The set of coupons was subjected to each of the tests shown in Table 2. The results on the tests showed no evidence or discoloration or corrosion.
  • Example 5 A series of flat coupons were cleaned, activated, and subsequently plated with 40 microinches of a nanocrystalline NiW alloy, 80 microinches of a nanocrystalline AgW alloy, and 3 microinches of rhodium. The set of coupons was subjected to each of the tests shown in Table 2. The results on the tests showed no evidence or discoloration or corrosion. Example 5
  • a series of flat coupons were cleaned, activated and subsequently plated with 40 microinches of nickel, 80 microinches of a nanocrystalline AgW alloy, and 3 microinches of rhodium.
  • the set of coupons was subjected to each of the tests shown in Table 2. The results on the tests showed no evidence or discoloration or corrosion.
  • Example 7 A series of flat coupons were cleaned, activated and subsequently plated with 40 microinches of a nanocrystalline NiW alloy, 80 microinches of a nanocrystalline AgW alloy, and 5 microinches of rhodium. The set of coupons was subjected to each of the tests shown in Table 2. The results on the tests showed no evidence or discoloration or corrosion.
  • Example 7 A series of flat coupons were cleaned, activated and subsequently plated with 40 microinches of a nanocrystalline NiW alloy, 80 microinches of a nanocrystalline AgW alloy, and 5 microinches of rhodium. The set of coupons was subjected to each of the tests shown in Table 2. The results on the tests showed no evidence or discoloration or corrosion. Example 7
  • a series of flat coupons were cleaned, activated, and subsequently plated with 40 microinches of a nanocrystalline NiW alloy deposit, 80 microinches of a nanocrystalline AgW alloy deposit, and 10 microinches of rhodium.
  • the set of coupons was subjected to the MFG and NSST tests shown in Table 2. The results on the tests showed localized corrosion. SEM/EDS inspection of samples prior to testing showed stress cracks in the Rhodium deposit.

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Abstract

L'invention concerne des articles revêtus et des procédés pour appliquer des revêtements comprenant une couche contenant du Rh et/ou du Ru. Dans certains cas, le revêtement peut présenter des propriétés et des caractéristiques souhaitables telles qu'une durabilité, une résistance à la corrosion et une conductivité élevée. Les articles sont revêtus, par exemple, à l'aide d'un procédé d'électrodéposition. Les articles peuvent comprendre un matériau de base, une couche barrière formée sur le matériau de base, une couche de métal formée sur la couche barrière, et une couche comprenant du Rh et/ou du Ru formée sur la couche métallique et présentant une épaisseur comprise entre approximativement 1 micropouce et approximativement 5 micropouces
PCT/US2014/044607 2013-07-01 2014-06-27 Articles revêtus comportant une couche métallique WO2015002838A1 (fr)

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EP3417089B1 (fr) * 2016-02-16 2023-12-13 Xtalic Corporation Articles comprenant un revêtement multicouche et procédés associés
WO2017143048A1 (fr) * 2016-02-16 2017-08-24 Xtalic Corporation Articles comprenant un revêtement sans nickel et procédés associés
USD896378S1 (en) 2016-12-22 2020-09-15 Integra Lifesciences Corporation Bipolar forceps
KR102630654B1 (ko) * 2017-05-01 2024-01-29 더 존스 홉킨스 유니버시티 나노트위닝된 니켈-몰리브덴-텅스텐 합금을 증착시키는 방법
CN107546515A (zh) * 2017-07-05 2018-01-05 启东乾朔电子有限公司 导电端子的制造方法及其用的电连接器

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110223442A1 (en) * 2010-03-12 2011-09-15 Xtalic Corporation Coated articles and methods
WO2012150133A2 (fr) * 2011-05-05 2012-11-08 Alchimer Procédé de dépôt de couches métalliques à base de nickel ou de cobalt sur un substrat solide semi-conducteur et trousse pour application dudit procédé
US20120328904A1 (en) * 2011-06-23 2012-12-27 Xtalic Corporation Printed circuit boards and related articles including electrodeposited coatings

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2486285A (en) * 1948-06-16 1949-10-25 Hazeltine Research Inc Electrical contact member
DE3027304C2 (de) * 1980-07-18 1982-09-30 Sds-Elektro Gmbh, 8024 Deisenhofen Elektrischer Mehrlagenkontakt
US5772451A (en) * 1993-11-16 1998-06-30 Form Factor, Inc. Sockets for electronic components and methods of connecting to electronic components
US20030199179A1 (en) * 1993-11-16 2003-10-23 Formfactor, Inc. Contact tip structure for microelectronic interconnection elements and method of making same
DE19530512C1 (de) * 1995-08-18 1996-10-17 Siemens Ag Elektrisches Schichtkontaktelement, Halbzeug für Schichtkontaktelemente und Verfahren zu seiner Herstellung

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110223442A1 (en) * 2010-03-12 2011-09-15 Xtalic Corporation Coated articles and methods
WO2012150133A2 (fr) * 2011-05-05 2012-11-08 Alchimer Procédé de dépôt de couches métalliques à base de nickel ou de cobalt sur un substrat solide semi-conducteur et trousse pour application dudit procédé
US20120328904A1 (en) * 2011-06-23 2012-12-27 Xtalic Corporation Printed circuit boards and related articles including electrodeposited coatings

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