US3234031A - Reduction nickel plating with boron reducing agents and organic divalent sulfur stabilizers - Google Patents

Reduction nickel plating with boron reducing agents and organic divalent sulfur stabilizers Download PDF

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Publication number
US3234031A
US3234031A US167959A US16795962A US3234031A US 3234031 A US3234031 A US 3234031A US 167959 A US167959 A US 167959A US 16795962 A US16795962 A US 16795962A US 3234031 A US3234031 A US 3234031A
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acid
thio
bath
plating
liter
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US167959A
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Zirngiebl Eberhard
Klein Heinz Gunter
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles

Definitions

  • the present invention is directed to an improved process of chemical metal plating of metal and plastic articles employing an aqueous bath containing salts of the metals to be deposited and boron compounds as reducing agents.
  • Chemical plating baths for the production of metal coatings on metal or plastic surfaces are known.
  • coating metals there are chiefly used nickel and/ or cobalt, but iron or zinc can also be deposited together with nickel and/ or cobalt.
  • Known reducing agnets are, besides alkali metal hypophosphites chiefly boron compounds with 1-4 hydrogen atoms directly linked with boron, for example, alkali metal borohydrides or alkylamine boranes.
  • salts or other compounds of metals of Groups IIb, IIIb, 1Vb, Vb, and/or VIb of the Periodic System of Elements may be added to these baths.
  • these baths tend to separate out metal flakes or to decompose with the formation of a black precipitate as soon as the concentration of the baths in plating metal has dropped by about 10 to in the course of plating.
  • these baths can be further used after filtration, but in most cases the plating stops after a short time and the baths must be discarded or worked up.
  • a bath of the composition g./liter of nickel chloride, g./liter of sodium hydroxide, g./liter of ethylenediamine, 0.6 g./liter of sodium borohydride, decomposes after 19.3% of the nickel employed have been used up from the bath by plating. Even after filtration of this bath, no further plating takes place.
  • Acidic baths moreover may contain buffer substances known as such, alkaline baths may contain complex formers known as such and, if desired, buffer substances.
  • these baths may furthermore contain additives of chemically linked metals of Groups Ilb, IIIb, IVb, Vb, and VIb of the Periodic System of Elements.
  • the reduction yields are likewise substantially improved by the addition of organic sulfur compounds soluble in the bath liquid.
  • a nickel bath having an initial concentration of 30 g./liter of nickel chloride, 40 g./liter of sodium hydroxide, 50 g./liter of ethylenediainine, 0.59 g./liter of sodium borohydride, the following values are obtained for the reduction yield as a function of the quantity of nickel deposited by plating:
  • organic sulfur compounds with formally bivalent sulfur to chemical plating baths leads not only to a considerable stabilization of the baths, but, in the case where mixed cobalt-nickel baths are used, also to a prefered deposition of nickel.
  • a solution of 45 g. Ni (NHQ CI 5 g. CoCl -6H O, 5 g. NH Cl and l g. NaBH, in 1 liter of 2 N ammonia solution yields at 50 C. on metal or plastic surfaces a Co-Ni-B coating containing 9.8% of nickel.
  • organic sulfur compounds with formally vivalent sulfur wherein the sulfur atom is directly linked oirzooolr Cmooorr om-oooNa CHZ COON8 SO NH
  • the organic sulfur compounds can be added to the plating baths individually or as mixtures. It is frequently of advantage to add one or more metal salts of Groups IIb, IlIb, IVb, Vb and/or Vlb of the Periodic System of Elements to the plating bath, in addition to the organic sulfur compounds. With these new baths metal and plastie surfaces can be plated more satisfactorily and economically than has hitherto been possible.
  • the content of the baths in salts of the plating metals such as chlorides, sulphates, acetates etc. of, for example, nickel, cobalt, nitrates and formiates corresponds to the values already known from borohydride-
  • reducing agents for the chemical depositing of metal there may be used for example:
  • Suitable solubilizers are methanol, ethanol, dioxan etc.
  • buffer substances for these new plating baths there may be used, for example, sodium acetate, sodium citrate, sodium tartrate etc.
  • Suitable complex formers for example, are ammonia and amines such as ethylene-diamine, ethanol-amine, tetramethylene diamine, diethylene triamine, triethylene tetramine, ethylenediamino tetraacetic acid, nitrilotriacetic acid.
  • Table 1 summarizes the basic concentration range of the bath components in accordance with this invention.
  • the organic sulfur compounds when incorporated in the plating bath, may be used in concentrations as high as 5 g./l., there is no improvement to be gained from the higher concentrations, and they are preferably used in the range of concentrations from about 0.01 to 1 g./l.
  • Metals such as nickel copper alloys, aluminum, iron as well as plastic material such as films, shectings, plates, fabrics and moulding articles from acetyl cellulose, celluloseacetobutyrate, polyvinyl-chloride, polyamidcs, polyurethanes, polystyrene, polycarbonates, polyacrylates, polyethylene and polypropylene.
  • the surface of these plastic articles may be activated by treating said surface with acids, alkali and metal salts, prior to plating.
  • EXAMPLE 1 In each of 5 chemical plating baths (a), (b), (c), (d), and (a) each of which contains 1 liter of bath liquor or borazane-containing baths.
  • the p13 ing of the metal plates sets in immediately after the addition of the reducing agent. After a plating time of 40 minutes, sodium borohydride can no longer be detected in any bath by iodometric analysis. Subsequently the plates are removed from the plating baths, rinsed, dried and the increase in weight is established.
  • EXAMPLE 3 In 1 liter of a chemical plating bath of a composition of 30 g./li-ter of nickel chloride, 40 g./liter of sodium hydroxide, 50 g./liter of ethylenediamine, 20 mg./liter of lead chloride, 160 rug/liter of 3-hydroxy-thionaphthenecarboxylicacid-(Z), there are. suspended 4 iron plates with a surface of 1 sq. dm./plate. The plates are previously. weighed. The bath is heated to 90 C. and treated with about 50 cc. of bath liquor containing 0.6175 g. 100%- NaBHrin solution. At intervals of 30 minutes one plate is withdrawn from the bathand a new weighed plate as well as 0.6175 g.
  • the total Ni deposit (4.9406 g.) corresponds to a reduction yield of 32.35%, calculated on the NaBH :consumption. 66.7% of the nickel present in the plating bath are deposited without decomposition of the bath.
  • EXAMPLE 4 a In 1 liter of a chemical plating bath of a composition of 30 g./liter of nickel chloride, 40 g./ liter of sodium hydroxide, 60 g./liter of ethylenediamine, 0.2 g./liter of thiodiglycollic acid, 0.1 g./liter of S-(Z-carboxyphenylY- thioglycollic acid, there are suspended 4 weighed iron plates with a surface of 1 sq. dm./plate; The addition of sodium borohydride is 0.5795 g. each time.
  • the working 8' method corresponds to that of Example 1. The following values are obtained:
  • Acetyl-cellulose foils are successively treatedin the following baths:
  • the baths are heated to 70 C. and 50 [111. of a Solution of 3.55 g. of diethylamine boraue in methanol are added to each bath.
  • the pH value of the plating baths is 5.0. Every 45 minutes the plates are exchanged for new metal plates, another 3.55 g. of diethylamine borane in 50 cc. of methanol being added each time.
  • the consumption of diethyl amine borane is determined iodometrically. This process is repeated four times. It can be seen already from the coloration of the baths, that cobalt is preferably deposited in the baths (a) and (b), whereas nickel is preferably deposited in the baths (c) and (d).
  • the metal coating deposited on the metal plates is removed with nitric acid and analysed as to its cobalt and nickel content. The reduction yields are established by means of the consumption of amine borane per charge and of the metal deposition on the copper and brass plates.
  • EXAMPLE 9 In each of three chemical plating baths (a), (b), (c), of the composition of 31 g./l. of nickel chloride, 45 g./1. of sodium hydroxide, 65 g./1. of etbylene-diamine and 0.6 g./l. of sodium borohydride are suspended four weighted copper plates with a surface of 1 sq. din/plate. To the baths (a) and (c) are added 0.01 g. and 0.016 g. of 4,4- dinitro-diphenylsullide-6,6-disulfonic acid, bath (a) contains no organic sulfur compound. The procedure is according to Example 1. Bath (a) is decomposed, when 14.5 percent of the nickel has been deposited. The baths (b) and (c) do not show any decomposition, when 50 percent of the nickel has been deposited.
  • Example 10 The chemical plating baths according to Example 7 show a decomposition after 20 minutes of working time.
  • a measure for the stabilization effect of the organic sulfur compounds mentioned in the Table 2 is the stability of these chemical plating baths containing said organic sulfur compounds in a bath composition according to Example 7.
  • Example 11 In a chemical plating bath, which has a temperatureof 90 C. and contains per, liter bath liquid 30 g. of nickel chloride (NiCl- --6H O)-,. 62 g. of ethylene diamine, 4'2 g. of sodium hydrazide, 1.0 g. of thio-diglycollic acid, 0.01 g. of lead chloride and 0.6 g. of sodium borohydride are suspended four metal plates. The proportion surface/volume of bath is 0.4.
  • a sodium borohydride solution consisting of 12 g. sodium: borohydride and 1 liter of a 2 naqueous solution of sodium hydroxide and 100 cm. per hour of a metal salt solution consisting of 118 g./l. of .nickel, chloride (NiCl 6ll O), 60 g./l. of ethylene-diamine, 1 g./l. .of thiodiglycollic acid and 0.1 g./l. of lead chloride.- Continuously 100 cm? of the bath liquid has been withdrawn per hour.
  • aqueous metal ;and :plastic plating .bath for plating by chemical reduction consisting essentially of aniaqueous solution of i (1) a plating metal selected from the group consisting of nickel, cobalt; and mixtures thereof in an amount of between 0.02' and 0.5 'mol per liter; (2) a boron compound selected fromithe group consisting of alkali metal borohydrides, trimethylamine borane, dimethyl amine xbon'ne',-. dimethyl amine. borane, diethyl. amine borane, and isopropyl amineborane in anamount of between 0.1 and 10 g. per.
  • a complex forming agent selected from the group consisting of: ammonia, ethylene 'diamine, ethanol amine, tetramethylene 'diamine,v diethylene triamine, triethylene tetra-amine, ethylene diamino-tetra-acetic acid, and nitrilo-triacetic acid in an amount of between 0.2 and 5 mols per litely-and.
  • At least one organic divalent sulfur compound selected from the group consisting of thio-diglycolic acid, fl-thio-dipropionic 'acid, -1,l'-thio-bis-(2,2,2- trichloro-ethanol); v(methylene-dithi'o)-diacetic acid,
  • acetylene-dithio-salicylic acid, 4,4-dinitro-diphenylsulfide-6,6'-disulfonic acid, 2,2f-thio-di(5-,aminobenzene sulfonic acid), Z-thio'phene carboxylic acid, 3,4-diphenyl-thiophene-2,5-dicarboxylic' acid, 3-hydroXy-thionaphthene-Z-carboxylic acid, Z-hydroxy: thionaphthene, 2 hydroxy 3 dibenzothiophenecarboxylic acid,- 2,3-thionaphthcnedion, '2-(p-aminophenyl)'-5-sulfo-6-bcnzothiazole :carboxylic acid, 2-1
  • Anaqueousmetal and plastic plating bath according toclaim'I additionally'containing. a member selected 5 from the group consisting'of methanol, ethanol, and? dioxane as solu'bilizer,.:.
  • aqueous metal and plastic plating bath accord-, ing to claim] additionally containinga member selected 2 from-the group consisting ,of sodium acetate, sodium nitrate, and sodium tartrate in anamount of between 5 I and 200 g. per liter,- as bufferingagent.
  • An aqueous metal andplasticplating bath according to-claim 1 additionally containing-in solution a lead salt in an amount of between 0.001 and 1 g. per liter..
  • a plating metal selected from the group consistingof nickel,%cobalt, and mixtures thereof in an amount of-between 0.02 and 0.5 ;mol per liter,
  • a boron compound selected from the group consisting of alkali metal borohydrides, trimethyl amine
  • a complex forming agent selected from the group consisting of ammonia, ethylene diamine, ethanol amine, tetra-methylene diamine, diethylene triamine, triethylene tetra-amine, ethylene diamino-tetra-acetic acid, and nitrilo triacetic acid in an amount of between 0.2 and mols per liter, and
  • said plating bath additionally contains a member selected from the group consisting of methanol, phenol, and dioxane as solubilizer.
  • said plating bath additionally contains a member selected from the group consisting of sodium acetate, sodium nitrate, and. sodium tartrate in an amount of between 5 and 200 g. per liter of buflering agent.
  • said plating bath additionally contains in solution a lead salt in an amount of between 0.001 and 1 g. per liter.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
US167959A 1961-02-04 1962-01-22 Reduction nickel plating with boron reducing agents and organic divalent sulfur stabilizers Expired - Lifetime US3234031A (en)

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DEF33143A DE1243493B (de) 1961-02-04 1961-02-04 Waessriges Bad zur chemischen Abscheidung von borhaltigen Metallueberzuegen

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BE (1) BE613430A (fr)
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GB (1) GB945018A (fr)

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3361580A (en) * 1963-06-18 1968-01-02 Day Company Electroless copper plating
US3372037A (en) * 1965-06-30 1968-03-05 Ibm Magnetic materials
US3379539A (en) * 1964-12-21 1968-04-23 Ibm Chemical plating
US3420680A (en) * 1966-04-08 1969-01-07 Shipley Co Compositions and processes for electroless nickel plating
US3454473A (en) * 1963-12-07 1969-07-08 Matsushita Electric Industrial Co Ltd Method for the manufacture of titanium anodic oxidation film capacitors having non-electrolytically plated cathode
US3485597A (en) * 1964-10-30 1969-12-23 Us Army Electroless deposition of nickel-phosphorus based alloys
US3497394A (en) * 1963-11-29 1970-02-24 Mc Donnell Douglas Corp Inorganic permselective membranes and method of making same
US3507681A (en) * 1967-06-02 1970-04-21 Mine Safety Appliances Co Metal plating of plastics
US3515564A (en) * 1968-05-27 1970-06-02 Allied Res Prod Inc Stabilization of electroless plating solutions
US3532541A (en) * 1967-06-19 1970-10-06 Ibm Boron containing composite metallic films and plating baths for their electroless deposition
US3661596A (en) * 1969-05-22 1972-05-09 Schering Ag Stabilized, chemical nickel plating bath
US4059217A (en) * 1975-12-30 1977-11-22 Rohr Industries, Incorporated Superalloy liquid interface diffusion bonding
EP0066073A1 (fr) * 1981-04-30 1982-12-08 Bayer Ag Produits textiles plats métallisés, pourvus de contacts électroconducteurs et leur préparation
US4368223A (en) * 1981-06-01 1983-01-11 Asahi Glass Company, Ltd. Process for preparing nickel layer
EP0084300A3 (fr) * 1982-01-19 1983-08-03 Axel Emil Bergström Méthode de métallisation de matériaux textiles
US4484988A (en) * 1981-12-09 1984-11-27 Richmond Metal Finishers, Inc. Process for providing metallic articles and the like with wear-resistant coatings
US4983428A (en) * 1988-06-09 1991-01-08 United Technologies Corporation Ethylenethiourea wear resistant electroless nickel-boron coating compositions
DE4311764A1 (de) * 1992-04-20 1993-10-21 Dipsol Chem Außenstromlose Metallabscheidungslösung und Metallabscheidungsverfahren mit dieser
US5403650A (en) * 1982-04-27 1995-04-04 Baudrand; Donald W. Process for selectively depositing a nickel-boron coating over a metallurgy pattern on a dielectric substrate and products produced thereby
US5624479A (en) * 1993-04-02 1997-04-29 International Business Machines Corporation Solution for providing catalytically active platinum metal layers
WO1997048832A3 (fr) * 1996-05-30 1998-02-26 Du Pont Procede de fabrication de monofilament ou fil polymere revetu de metal thermiquement stable
US5855959A (en) * 1992-04-06 1999-01-05 International Business Machines Corporation Process for providing catalytically active platinum metal layers
US6045680A (en) * 1996-05-30 2000-04-04 E. I. Du Pont De Nemours And Company Process for making thermally stable metal coated polymeric monofilament or yarn
US20020142196A1 (en) * 2001-01-03 2002-10-03 More Energy Ltd. Liquid fuel compositions for electrochemical fuel cells
US20060083850A1 (en) * 2004-10-18 2006-04-20 Enthone Inc. Cobalt and nickel electroless plating in microelectronic devices
US20070160857A1 (en) * 2005-12-29 2007-07-12 Sang-Chul Lee Cobalt-based alloy electroless planting solution and electroless plating method using the same
US20110192316A1 (en) * 2010-02-05 2011-08-11 E-Chem Enterprise Corp. Electroless plating solution for providing solar cell electrode
US10294569B2 (en) * 2017-10-06 2019-05-21 Rohm And Haas Electronic Materials Llc Stable electroless copper plating compositions and methods for electroless plating copper on substrates
TWI686508B (zh) * 2017-10-06 2020-03-01 美商羅門哈斯電子材料有限公司 穩定的化學鍍銅組合物及在襯底上化學鍍銅之方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1266099B (de) * 1965-02-20 1968-04-11 Schering Ag Bad fuer die reduktive Kupferabscheidung
DE3622090C1 (fr) * 1986-07-02 1990-02-15 Blasberg-Oberflaechentechnik Gmbh, 5650 Solingen, De

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GB626999A (en) * 1946-03-22 1949-07-25 Teletype Corp An improved mechanism particularly applicable to printing telegraph apparatus
US2528902A (en) * 1947-06-12 1950-11-07 Harshaw Chem Corp Bright nickel plating
US2844530A (en) * 1957-02-15 1958-07-22 Int Nickel Co Black nickel plating
GB836480A (en) * 1957-01-15 1960-06-01 Du Pont Improvements in or relating to alloy plate
US2994369A (en) * 1959-04-02 1961-08-01 Pittsburgh Plate Glass Co Nickel plating chemical composition
US3062666A (en) * 1958-11-26 1962-11-06 Du Pont Bath compositions for the chemical reductive plating of nickel-boron and cobalt-boron alloys
US3096182A (en) * 1958-10-01 1963-07-02 Du Pont Chemical plating solution and process for plating therewith

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US2762723A (en) * 1953-06-03 1956-09-11 Gen American Transporation Cor Processes of chemical nickel plating and baths therefor
GB842826A (en) * 1957-11-15 1960-07-27 Du Pont Improvements in or relating to chemical plating

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GB626999A (en) * 1946-03-22 1949-07-25 Teletype Corp An improved mechanism particularly applicable to printing telegraph apparatus
US2528902A (en) * 1947-06-12 1950-11-07 Harshaw Chem Corp Bright nickel plating
GB836480A (en) * 1957-01-15 1960-06-01 Du Pont Improvements in or relating to alloy plate
US2844530A (en) * 1957-02-15 1958-07-22 Int Nickel Co Black nickel plating
US3096182A (en) * 1958-10-01 1963-07-02 Du Pont Chemical plating solution and process for plating therewith
US3062666A (en) * 1958-11-26 1962-11-06 Du Pont Bath compositions for the chemical reductive plating of nickel-boron and cobalt-boron alloys
US2994369A (en) * 1959-04-02 1961-08-01 Pittsburgh Plate Glass Co Nickel plating chemical composition

Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3361580A (en) * 1963-06-18 1968-01-02 Day Company Electroless copper plating
US3497394A (en) * 1963-11-29 1970-02-24 Mc Donnell Douglas Corp Inorganic permselective membranes and method of making same
US3454473A (en) * 1963-12-07 1969-07-08 Matsushita Electric Industrial Co Ltd Method for the manufacture of titanium anodic oxidation film capacitors having non-electrolytically plated cathode
US3485597A (en) * 1964-10-30 1969-12-23 Us Army Electroless deposition of nickel-phosphorus based alloys
US3379539A (en) * 1964-12-21 1968-04-23 Ibm Chemical plating
US3372037A (en) * 1965-06-30 1968-03-05 Ibm Magnetic materials
US3420680A (en) * 1966-04-08 1969-01-07 Shipley Co Compositions and processes for electroless nickel plating
US3507681A (en) * 1967-06-02 1970-04-21 Mine Safety Appliances Co Metal plating of plastics
US3532541A (en) * 1967-06-19 1970-10-06 Ibm Boron containing composite metallic films and plating baths for their electroless deposition
US3515564A (en) * 1968-05-27 1970-06-02 Allied Res Prod Inc Stabilization of electroless plating solutions
US3661596A (en) * 1969-05-22 1972-05-09 Schering Ag Stabilized, chemical nickel plating bath
US4059217A (en) * 1975-12-30 1977-11-22 Rohr Industries, Incorporated Superalloy liquid interface diffusion bonding
EP0066073A1 (fr) * 1981-04-30 1982-12-08 Bayer Ag Produits textiles plats métallisés, pourvus de contacts électroconducteurs et leur préparation
US4368223A (en) * 1981-06-01 1983-01-11 Asahi Glass Company, Ltd. Process for preparing nickel layer
US4484988A (en) * 1981-12-09 1984-11-27 Richmond Metal Finishers, Inc. Process for providing metallic articles and the like with wear-resistant coatings
EP0084300A3 (fr) * 1982-01-19 1983-08-03 Axel Emil Bergström Méthode de métallisation de matériaux textiles
US5565235A (en) * 1982-04-27 1996-10-15 Baudrand; Donald W. Process for selectively depositing a nickel-boron coating over a metallurgy pattern on a dielectric substrate
US5403650A (en) * 1982-04-27 1995-04-04 Baudrand; Donald W. Process for selectively depositing a nickel-boron coating over a metallurgy pattern on a dielectric substrate and products produced thereby
US4983428A (en) * 1988-06-09 1991-01-08 United Technologies Corporation Ethylenethiourea wear resistant electroless nickel-boron coating compositions
US5855959A (en) * 1992-04-06 1999-01-05 International Business Machines Corporation Process for providing catalytically active platinum metal layers
FR2690171A1 (fr) * 1992-04-20 1993-10-22 Dipsol Chem Solution de dépôt chimique de nickel ou d'un alliage de nickel et son procédé d'utilisation.
DE4311764A1 (de) * 1992-04-20 1993-10-21 Dipsol Chem Außenstromlose Metallabscheidungslösung und Metallabscheidungsverfahren mit dieser
DE4311764C2 (de) * 1992-04-20 2002-04-11 Dipsol Chem Außenstromlose Metallabscheidungslösung und Metallabscheidungsverfahren mit dieser
US5624479A (en) * 1993-04-02 1997-04-29 International Business Machines Corporation Solution for providing catalytically active platinum metal layers
WO1997048832A3 (fr) * 1996-05-30 1998-02-26 Du Pont Procede de fabrication de monofilament ou fil polymere revetu de metal thermiquement stable
US6045680A (en) * 1996-05-30 2000-04-04 E. I. Du Pont De Nemours And Company Process for making thermally stable metal coated polymeric monofilament or yarn
US20060183008A1 (en) * 2001-01-03 2006-08-17 More Energy Ltd. Liquid fuel compositions for electrochemical fuel cells
US20020142196A1 (en) * 2001-01-03 2002-10-03 More Energy Ltd. Liquid fuel compositions for electrochemical fuel cells
US20060083850A1 (en) * 2004-10-18 2006-04-20 Enthone Inc. Cobalt and nickel electroless plating in microelectronic devices
US7332193B2 (en) 2004-10-18 2008-02-19 Enthone, Inc. Cobalt and nickel electroless plating in microelectronic devices
US20070160857A1 (en) * 2005-12-29 2007-07-12 Sang-Chul Lee Cobalt-based alloy electroless planting solution and electroless plating method using the same
US7758681B2 (en) * 2005-12-29 2010-07-20 Lg Chem, Ltd. Cobalt-based alloy electroless plating solution and electroless plating method using the same
US20110192316A1 (en) * 2010-02-05 2011-08-11 E-Chem Enterprise Corp. Electroless plating solution for providing solar cell electrode
US10294569B2 (en) * 2017-10-06 2019-05-21 Rohm And Haas Electronic Materials Llc Stable electroless copper plating compositions and methods for electroless plating copper on substrates
TWI686508B (zh) * 2017-10-06 2020-03-01 美商羅門哈斯電子材料有限公司 穩定的化學鍍銅組合物及在襯底上化學鍍銅之方法
US10655227B2 (en) * 2017-10-06 2020-05-19 Rohm And Haas Electronic Materials Llc Stable electroless copper plating compositions and methods for electroless plating copper on substrates

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Publication number Publication date
CH412513A (de) 1966-04-30
BE613430A (fr) 1962-05-29
GB945018A (en) 1963-12-18
DE1243493B (de) 1967-06-29

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