US20130228465A1 - Composites of carbon black and metal - Google Patents

Composites of carbon black and metal Download PDF

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US20130228465A1
US20130228465A1 US13/784,009 US201313784009A US2013228465A1 US 20130228465 A1 US20130228465 A1 US 20130228465A1 US 201313784009 A US201313784009 A US 201313784009A US 2013228465 A1 US2013228465 A1 US 2013228465A1
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carbon black
particles
silver
metal
nano
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Wan Zhang-Beglinger
Linda STAPPERS
Jan Fransaer
Michael P. Toben
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Rohm and Haas Electronic Materials LLC
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Priority to US14/748,599 priority patent/US20150292105A1/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • 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
    • 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
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • 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
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • 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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/48—Electroplating: Baths therefor from solutions of gold
    • 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
    • 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
    • C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/10—Agitating of electrolytes; Moving of racks
    • 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
    • C25D5/04—Electroplating with moving electrodes
    • 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
    • C25D5/20—Electroplating using ultrasonics, vibrations

Definitions

  • the present invention is directed to composites of carbon black particles and metal. More specifically, the present invention is directed to composites of carbon black particles and metal where the carbon black particles are in the nanometer range.
  • Composite plating is a technology well documented and widely practiced in both electrolytic and electroless plating.
  • Composite plating refers to the inclusion of particulate matter within a metal plated layer.
  • the development and acceptance of composite plating stems from the discovery that the inclusion of particles within a metal plated layer can enhance various properties of the metal plated layer and in many situations actually provide entirely new properties to the metal layer.
  • Particles of various materials can provide characteristics to the metal layer including wear resistance, lubricity, corrosion resistance, phosphorescence, friction altered appearances and other properties.
  • JP09-007445 discloses a sliding contact electric component which has an electroplated coating film of graphite particles dispersed in a silver metal matrix.
  • particles of SiC, WC, ZrB, Al 2 O 3 , ZrO 2 and Cr 2 O 3 may also be incorporated into the composite.
  • particles of TiO 2 , ThO 2 , MoO 3 , W 2 C, TiC, B 4 C and CrB 2 may be included to increase the hardness of the deposited coating.
  • U.S. Pat. No. 6,635,166 discloses an electrolytic composite plating method.
  • the patent discloses particles of SiC, glass, kaolin, corundum, Si 3 N 4 , various metal oxides, graphite, graphite fluoride, various colorants and other metal compounds such as compounds of W, Mo and Ti.
  • Metals which may be electroplated with such particles include, for example, silver, gold, nickel, copper, zinc, tin, lead, chromium and alloys thereof.
  • azo-surfactants are included in the composite plating formulations to enable an increase in the content of the particles in the electroplating bath.
  • U.S. Pat. No. 7,514,022 discloses a composite of silver and graphite particles used to electroplate a coating on switches and connectors.
  • the graphite particles range in size from 0.1 ⁇ m to 1.0 ⁇ m.
  • Additives such as dispersing agents are excluded from the formulation. Although including dispersing agents or surfactants in composite plating baths may increase the content of fine particles to some extent, the dispersing agent effect is known to be limited. It is believed that the dispersing agent or surfactant remains as it is on the fine particles which have been deposited by electroplating in the adsorbed state. This is believed to inhibit other fine particles from being deposited. Instead the graphite particles are oxidized to achieve the desired dispersion of particles in the silver electroplating baths.
  • Such oxidizing agents include nitric acid, hydrogen peroxide, potassium permanganate, potassium persulfate, sodium persulfate and sodium perchlorate.
  • compositions include one or more sources of metal ions and carbon black nano-particles.
  • methods include providing a composition including one or more sources of metal ions and carbon black nano-particles; contacting a substrate with the composition; and electroplating a composite of one or more metals and carbon black nano-particles onto the substrate.
  • articles include a composite including one or more metals and carbon black nano-particles dispersed within the one or more metals.
  • compositions are substantially stable dispersions of carbon black nano-particles and metal ions which can be electroplated on various substrates to form coatings of composites of metal or metal alloy having substantially uniform dispersions of the carbon black nano-particles throughout a metal or metal alloy matrix.
  • the composites are electrically conductive and provide good wear resistance with improved durability in comparison to many conventional metal and metal alloy coatings.
  • the composite coatings may be used to replace hard gold coatings of gold/cobalt and gold/nickel which are often used to coat articles which are exposed to rigorous wear cycles or are prone to oxidation due to heat in sliding processes, such as is typical in switches and connectors.
  • FIG. 1 is a SEM at 3500 ⁇ of a cross-section of a composite of silver and graphite particles.
  • FIG. 2 is a SEM at 5000 ⁇ of a cross-section of a composite of silver and carbon black nano-particles.
  • FIG. 3 is a graph of contact resistance in mOhm versus contact forces in cN of a silver and silver and carbon black nanoparticles.
  • FIG. 4 is a SEM at 10,000 ⁇ of a cross section of a composite of silver and carbon black nano-particles.
  • Compositions are aqueous dispersions of carbon black nano-particles and one or more sources of metal ions.
  • Carbon black is an amorphous form of carbon with a high surface area to volume ratio and is electrically conductive.
  • diamond and graphite are crystalline in structure. Diamond has a tetrahedral configuration.
  • Graphite has a layered, planar crystal structure where each carbon atom is bonded to three other carbons forming a hexagonal structure.
  • Graphite is much softer than diamond and the layered, planar type structure facilitates easy cleavage along the planes which makes it desirable as a solid lubricant but is not very durable in coatings which are exposed to rigorous wear cycles. In general, it has a relatively low coefficient of friction.
  • Carbon black nano-particles have an average diameter range from 5 nm to 500 nm, preferably from 10 nm to 250 nm, more preferably from 15 nm to 100 nm and most preferably from 15 nm to 30 nm
  • the carbon black nano-particles are spherical or elliptical in shape, not fibers or nano-tubes.
  • Carbon black may be obtained from various commercial sources or prepared by one or more conventional methods known in the art. Carbon black may be produced industrially, for example, by the incomplete combustion of heavy petroleum products such as coal tar and ethylene cracking tar.
  • a commercially available source of carbon black is Degussa® Carbon Black (available from Orion Engineered Carbons, Germany).
  • the commercially available carbon black is agglomerated and is not within the desired particle size range. Accordingly, to achieve the desired particle size range the agglomerated carbon black particles may be de-agglomerated using ultrasonic methods and apparatus well known in the art.
  • the carbon black nano-particles may be added to an aqueous solution of one or more water-soluble metal salts which may include one or more surfactants and conventional additives found in metal plating baths.
  • the surfactants are added to the water first then the carbon black nano-particles are added and this mixture is added to the plating bath.
  • the carbon black nano-particles may also be mixed in commercially available metal electroplating baths. The components of the bath are typically mixed using high power ultrasonic laboratory mixing apparatus to achieve a substantially uniform dispersion of carbon black nano-particles and plating bath components.
  • Carbon black nano-particles are included in the metal electroplating baths in amounts of at least 1 g/L, preferably at least 10 g/L, more preferably from 20 g/1 to 200 g/l, most preferably from 50 g/L to 150 g/L.
  • Metals which may be co-deposited with the carbon black nano-particles are provided by one or more sources of water-soluble metal salts. Although silver is the most preferred metal for forming the composite with the carbon black nano-particles, it is envisioned that other metals and metal alloys may be used to form the composites.
  • Water-soluble metal salts which provide metal ions for the deposition of metals include, but are not limited to, silver, gold, palladium, tin, indium, copper and nickel. Such water-soluble metal salts are generally commercially available from a variety of suppliers or may be prepared by methods well known in the art. It is envisioned that alloys of such metals may also be co-deposited with the carbon black nano-particles.
  • Such alloys may include, but are not limited to, tin/silver, tin/copper, palladium/nickel and tin/silver/copper.
  • the metal co-deposited with the carbon black nano-particles is silver, gold, palladium, tin or palladium/nickel alloy. More preferably the metal co-deposited with the carbon black nano-particles is silver or tin. Most preferably the metal co-deposited with the carbon black nano-particles is silver.
  • one or more sources of metal ions are included in the electroplating baths in amounts of 0.1 g/L to 200 g/L.
  • Sources of silver ions include, but are not limited to, silver oxide, silver nitrate, silver sodium thiosulfate, silver cyanide, silver gluconate; silver-amino acid complexes such as silver-cysteine complexes; silver alkyl sulfonates, such as silver methane sulfonate and silver hydantoin and silver succinimide compound complexes.
  • silver cyanide may be a source of silver ions, preferably silver and silver alloy electroplating baths are cyanide-free.
  • the sources of silver ions are included in the aqueous baths in amounts of 1 g/L to 150 g/L.
  • Sources of gold ions include, but are not limited to, gold salts which provide gold (I) ions.
  • Such sources of gold (I) ions include, but are not limited to, alkali gold cyanide compounds such as potassium gold cyanide, sodium gold cyanide, and ammonium gold cyanide, alkali gold thiosulfate compounds such as trisodium gold thiosulfate and tripotassium gold thiosulfate, alkali gold sulfite compounds such as sodium gold sulfite and potassium gold sulfite, ammonium gold sulfite, and gold (I) and gold (III) halides such as gold (I) chloride and gold (III) trichloride.
  • the alkali gold cyanide compounds are used such as potassium gold cyanide.
  • the amount of gold salts ranges from 1 g/L to 50 g/L.
  • palladium compounds may be used as a source of palladium ions.
  • Such palladium compounds include, but are not limited to, palladium complex ion compounds with ammonia as the complexing agent.
  • Such compounds include, but are not limited to, dichlorodiammine palladium (II), dinitrodiammine palladium (II), tetrammine palladium (II) chloride, tetrammine palladium (II) sulfate, tetrammine palladium tetrachloropalladate, tetramine palladium carbonate and tetramine palladium hydrogen carbonate.
  • palladium compounds include, but are not limited to, palladium dichloride, palladium dibromide, palladium sulfate, palladium nitrate, palladium monoxide-hydrate, palladium acetates, palladium propionates, palladium oxalates and palladium formates.
  • Palladium compounds are included in the plating compositions is amounts of 10 g/L to 50 g/L.
  • Water-soluble nickel salts include, but are not limited to, halides, sulfates, sulfites and phosphates. Typically, the nickel halide and sulfate salts are used. Water-soluble nickel salts are included in amounts of 0.1 g/L to 150 g/L.
  • Water-soluble tin compounds include, but are not limited to salts, such as tin halides, tin sulfates, tin alkane sulfonates and tin alkanol sulfonates. When tin halide is used, it is typical that the halide is chloride.
  • the tin compound is typically tin sulfate, tin chloride or tin alkane sulfonate, and more typically tin sulfate or tin methane sulfonate. Tin salts are included in the compositions in amounts of 5 to 100 g/L.
  • Water-soluble copper salts include without limitation: copper sulfate; copper halides such as copper chloride; copper acetate; copper nitrate; copper fluoroborate; copper alkylsulfonates; copper arylsulfonates; copper sulfamate; and copper gluconate.
  • Exemplary copper alkylsulfonates include copper (C 1 -C 6 )alkylsulfonate and more typically copper (C 1 -C 3 )alkylsulfonate.
  • the copper salt is included in amounts of 10 g/L to 180 g/L of plating composition.
  • Sources of indium ions include, but are not limited to, indium salts of alkane sulfonic acids and aromatic sulfonic acids, such as methanesulfonic acid, ethanesulfonic acid, butane sulfonic acid, benzenesulfonic acid and toluenesulfonic acid, salts of sulfamic acid, sulfate salts, chloride and bromide salts of indium, nitrate salts, hydroxide salts, indium oxides, fluoroborate salts, indium salts of carboxylic acids, such as citric acid, acetoacetic acid, glyoxylic acid, pyruvic acid, glycolic acid, malonic acid, hydroxamic acid, iminodiacetic acid, salicylic acid, glyceric acid, succinic acid, malic acid, tartaric acid, hydroxybutyric acid, indium salts of amino acids, such as arginine, aspartic
  • the electroplating baths optionally include one or more conventional additives typically included in metal electroplating baths.
  • additives may vary depending on the type of metal to be plated.
  • Such additives are well known in the art and the literature.
  • conventional additives include, but are not limited to, complexing agents and chelating agents for metal ions, suppressors, levelers, stabilizers, antioxidants, grain refiners, buffers to maintain the pH of the electroplating bath, electrolytes, acids, bases, salts of acids and bases, surfactants and dispersing agents.
  • the pH of the electroplating baths may range from less than 1 to 14, typically, the pH ranges from 1 to 12, more typically from 3 to 10.
  • the pH depends on the particular metal or metal alloy to be co-deposited with the carbon black nano-particles as well as the other bath components.
  • Conventional inorganic and organic acids and bases may be used to modify the pH.
  • the carbon black nano-particle and metal electroplating baths may include one or more surfactants to assist in providing a uniform dispersion of carbon black nano-particles.
  • surfactants may be included in the baths in amounts of 1 g/L to 100 g/L, preferably from 1 g/L to 60 g/L.
  • Such surfactants include, but are not limited to, secondary alcohol ethoxylates, EO/PO copolymers, beta-naphthol ethoxylates, alkyl ether phosphates, also known as alcohol phosphate esters, and alkyldiphenyloxide disulfonates, and surfactants such as cetyltrimethylammonium hydrogensulfate and quaternary polyvinylimidazole.
  • fluorocarbon polymers such as tetrafluoroethylene fluorocarbon polymers, are included in the plating bath.
  • surfactants examples include TERGITOLTM XD EO/PO copolymer, POLYMAXTM PA-31 ethoxylated beta-naphthol, BASOTRONICTM PVI quaternary polyvinylimidazole, and TEFLONTM tetrafluoroethylene fluorocarbon polymers.
  • Exemplary alcohol phosphate esters have a general formula:
  • the silver electroplating bath preferably includes such alcohol phosphate esters.
  • compositions of carbon black nano-particles and one or more metal ions may be electroplated onto substrates using conventional electroplating methods.
  • current densities may range from 0.1 ASD and greater.
  • current densities range from 0.1 ASD to 100 ASD.
  • current densities range from 0.1 ASD to 10 ASD.
  • Composition temperatures during electroplating may range from room temperature to 90° C.
  • the substrates may be immersed in the electroplating bath, such as in vertical electroplating or by horizontal plating where the substrate is placed on a conveyor and the bath is sprayed onto the substrate.
  • the electroplating bath is agitated during plating usually through pumping the plating solution within the tank or in the case of reel-to-reel plating pumping the solution from the sump tank to the plating cell.
  • Reel-to-reel plating allows for select plating of metal.
  • Various reel-to-reel apparatus are known by those of skill in the art. The method can plate strips of manufactured products or reels of raw material before they are stamped into parts.
  • the electroplating bath may also be agitated using ultrasound with conventional ultrasound apparatus.
  • Electroplating times vary depending on the type of metal or metal alloy to be co-deposited with the carbon black nano-particles.
  • the deposited composites are a matrix of metal or metal alloy with carbon black nano-particles substantially uniformly dispersed throughout the metal or metal alloy matrix.
  • the composites have a matrix of silver, gold, palladium, tin or palladium/nickel alloy. More preferably the composites have a matrix of silver or tin. Most preferably the composites have a silver matrix.
  • Composite thicknesses may vary depending on the metal or metal alloy and the function of the substrate plated. In general, composite thicknesses are at least 0.1 ⁇ m, typically from 1 ⁇ m to 1000 ⁇ m.
  • the composite has a thickness of 0.5 ⁇ m to 100 ⁇ m, more preferably from 1 ⁇ m to 50 ⁇ m.
  • the composites may be electroplated adjacent conductive surfaces of various types of substrates. Such conductive surfaces include, but are not limited to, copper, copper alloys, nickel, nickel alloys, tin and tin alloys.
  • the composites are electrically conductive and provide a wear resistant deposit with improved durability in comparison to many conventional metal and metal alloy coatings.
  • the composite coatings may be used to replace hard gold coatings of gold/cobalt and gold/nickel which are often used to coat articles which are exposed to rigorous wear cycles or are prone to oxidation due to heat in sliding processes, such as is typical in switches and connectors.
  • An aqueous silver electroplating solution was prepared as shown in the table below.
  • Graphite nano-particles supplied by Nanostructured & Amorphous Materials Inc having an average diameter of 400 nm at a concentration of 20 g/L were mixed with the silver electroplating bath.
  • a clean copper rotating disk cathode was immersed into the solution and was connected to a rectifier.
  • the counter electrode was a silver anode.
  • the temperature of the silver electroplating bath was maintained at 60° C. during silver composite electroplating.
  • the current density was 1 ASD.
  • Electroplating was done until a layer of silver 25 ⁇ m thick was deposited on the copper rotating disk. The silver plated disk was removed from the electroplating bath and rinsed with deionized water at room temperature.
  • a UP400S 400 Watt full amplitude ultrasonic probe supplied by Hielscher Ultrasonics, Germany, was inserted in the vicinity of the cathode prior to and during the electroplating, at 60% amplitude and 0.5 duty cycle.
  • FIG. 1 is a SEM image (secondary electrons) of a cross-section of the composite layer on the copper substrate at 3500 ⁇ , obtained using secondary electrons. The dark sections or bands indicate where graphite nano-particles were incorporated into the silver metal matrix. As is evidenced by the SEM the nano-particle incorporation was both sparse and not homogeneous. The nano-particles of graphite agglomerated in the composite.
  • Example 2 The method of Example 1 was repeated except that 5 g/L of carbon black nano-particles with an average diameter of 25 nm (available from Orion Engineered Carbons) were mixed with the silver electroplating bath in Table 2. The plating parameters were the same as described above.
  • FIG. 2 is a 5000 ⁇ SEM cross-section (back scattered electrons) of the composite. The dark sections indicate areas where the nano-particles of carbon black were incorporated into the silver matrix. As is evident from the SEM in FIG. 2 substantial amounts of nano-particles were incorporated into the silver matrix. The incorporation was homogeneous in contrast to the graphite incorporation of Example 1.
  • an ultrasonic probe UP400S was inserted in the vicinity of the cathode prior to and during the electroplating at 60% amplitude and 0.5 duty cycle. Electroplating was done until a layer of silver or silver composite of 25 um thick was deposited on the copper rotating disks. The plated disks were removed from the electroplating baths and rinsed with deionized water at room temperature.
  • FIG. 3 shows the contact resistance in mOhms of both the composite of silver and carbon black nano-particles (AgCB) and the silver (Ag), under varied contact forces in centiNewtons. The results indicated that the contact resistance of the silver and carbon black nano-particles composite remained substantially the same as the silver deposit over the various forces applied.
  • Example 2 The method of Example 2 was repeated with 50 g/L of carbon black nano-particles. Instead of using ultrasonic disintegration, a surfactant was added into the plating solution to facilitate the particle dispersion.
  • the bath formulation was as disclosed in Table 3. The plating parameters were the same as described above in Example 2.
  • FIG. 4 is a 10,000 ⁇ SEM cross-section of the composite. The dark sections indicate areas where the nano-particles of carbon black were incorporated into the silver matrix. As is evident from the SEM in FIG. 4 substantial amounts of nano-particles were incorporated into the silver matrix. The incorporation was homogeneous in contrast to the graphite incorporation of Example 1.

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  • Materials Engineering (AREA)
  • Metallurgy (AREA)
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Cited By (8)

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US20150176137A1 (en) * 2013-12-20 2015-06-25 University Of Connecticut Methods for preparing substrate cored-metal layer shelled metal alloys
US20170158980A1 (en) * 2014-05-16 2017-06-08 Ab Nanol Technologies Oy Composition
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US20150176137A1 (en) * 2013-12-20 2015-06-25 University Of Connecticut Methods for preparing substrate cored-metal layer shelled metal alloys
US20170158980A1 (en) * 2014-05-16 2017-06-08 Ab Nanol Technologies Oy Composition
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US11021804B2 (en) * 2018-01-26 2021-06-01 Samsung Electronics Co., Ltd. Plating solution and metal composite and method of manufacturing the same
US20210366628A1 (en) * 2018-03-16 2021-11-25 Nexans Process for manufacturing a carbon-metal composite material and use thereof for manufacturing an electric cable
US11646125B2 (en) * 2018-03-16 2023-05-09 Nexans Process for manufacturing a carbon-metal composite material and use thereof for manufacturing an electric cable
US11234456B2 (en) * 2018-08-13 2022-02-01 China Tobacco Yunnan Industrial Co., Ltd Modified carbon material and method for reducing carbonaceous material ignition temperature
US11225726B2 (en) * 2019-01-22 2022-01-18 Dowa Metaltech Co., Ltd. Composite plated product and method for producing same
CN111705340A (zh) * 2019-03-18 2020-09-25 同和金属技术有限公司 复合镀覆制品及其制造方法
EP4328933A1 (fr) * 2022-08-26 2024-02-28 TE Connectivity Solutions GmbH Revêtement sur une surface pour transmettre un courant électrique
EP4328934A1 (fr) * 2022-08-26 2024-02-28 TE Connectivity Solutions GmbH Revêtement sur une surface pour transmettre un courant électrique

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CN103290457B (zh) 2016-03-16
TWI539034B (zh) 2016-06-21
EP2634293A2 (fr) 2013-09-04
CN103290457A (zh) 2013-09-11
KR20130100756A (ko) 2013-09-11
JP2013216971A (ja) 2013-10-24
EP2634293B1 (fr) 2018-07-18
TW201348519A (zh) 2013-12-01

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