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Publication numberUS3294578 A
Publication typeGrant
Publication dateDec 27, 1966
Filing dateOct 22, 1963
Priority dateOct 22, 1963
Publication numberUS 3294578 A, US 3294578A, US-A-3294578, US3294578 A, US3294578A
InventorsPopeck Stanley P
Original AssigneeGen Aniline & Film Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Deposition of a metallic coat on metal surfaces
US 3294578 A
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Description  (OCR text may contain errors)

United States Patent 3,294,578 DEPOSITION OF A METALLIC COAT 0N METAL SURFACES Stanley P. Popeck, Nimmonsburg, N.Y., assignor to General Aniline & Film Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed Oct. 22, 1963, Ser. No. 318,102

6 Claims. (Cl. 117-130) This invention relates to a new and novel process of depositing a metallic coat on metallic surfaces.

I have discovered that cations of copper, gold, palladium, platinum, silver and te-llurium derived from a compound containing an anion such as oxide, hydroxide, carbonate, chloride, bromide, iodide, etc., form complexes with certain nitrogen containing compounds in the presence either of hydrobromic or hydroiodic acid. These complexes deposit the metal cation of the complex when in contact with a metal which is aboxe the complexed metal cation in the electromotive series including alloys thereof such as yellow brass, soft iron, stainless steel, bronze, and the like. The unusual feature of applying these complexes is that they give a hard plating or coating of the metal without resorting to an electrical current. The plating of metals with the complexes is so rapid that within seconds a metallic coating is observed whereas within seconds a durable plate is deposited at a temperature ranging from ambient to 100 C. The most outstanding feature is that there is no need to degrease the metal to be plated and in fact no buffing or polishing prior to plating is necessary. The silver and gold plate, however, may be polished with finely pulverized sodium bicarbonate, calcium carbonate or other common polishing agent such as diatomaceous earth.

The nitrogen containing compounds which may be employed to form the complexes are characterized by the following formulae:

(1) H20GH2 H2C\ /C=O N i N R R1 R1C ON/ and wherein R and R represent either hydrogen or an alkyl of from 1 to 4 carbon atoms, and R and R represent an alkyl of from 1 to 4 carbon atoms.

As examples of nitrogen containing compounds of the foregoing formulae, which are used as such or in admixture for complexing with compounds containing the aforementioned metal cations, the following are illustrative:

2-pyrrolidone 5-methyl-2-pyrrol-idone N-methyl-Zpyrrolidone N-ethyl-Z-pyrrolidone N-isopropyl-Z-pyrrolidone N-butyl-Z-pyrrolid-one N,N-dimethyl formamide N,N-diethyl formamide N,N-dipropy-l formamide N,N-disopropyl formamide N,N-dibutyl formamide N,N-dimethyl acetamide N,N-diethyl acetamide N,N-dipropyl acetamide N,N-dibutyl acetamide N,N-dim'ethyl propi-onamide N,N-diethyl propion'amide N,N-dipropyl propionamide N,N-dibutyl propionamide N,N-dimethyl butyramide N,N-diethyl butyramide N,N-dipropy'l butyramide N,N-dibutyl butynamide Aniline N-dimethyl aniline N-diethyl aniline N-dipropyl aniline N-dibutyl aniline Dimethyl amine Diethyl amine Dipropyl amine 1 Dibutyl amine Trimethyl amine Triethyl amine Tripropyl Iamine Tributyl amine In addition to the foregoing, I found that pyridine,, pyrrole, pyr-ro'l-ine, py-rrolidine, pyrimidine, quinoline, etc. as well as mixtures thereof are also useful in forming the complexes.

In forming the complex, where the halides of the aforementioned metals are used, one mode of the metal halide is treated at room temperature with one mole in excess of the nitrogen containing compound in liquid form to cover the solid halide salt followed by the addition of one mole of either hydrobromic or hydroiodic acid. The copper and gold halides may be either in their ous or ic form. After stirring for a few minutes at room temperature, until solution is reached, one part by weight of the resulting solution of the complex is then added to 1-4 parts by weight or volume of the nitrogen containing compound which may be the same as initially employed or any one or a mixture of the above enumerated compounds. In the event the nitrogen containing compound is a solid at room temperature a mole thereof in excess is used to cover the solid halide salt followed by the addition of either the hydrobromic or hydroiodic acid with stirring. The mixture during stirring is heated at a temperature ranging from 35 C. to C. until a solution is reached. One part by weight of the resulting solution is then added to 1-4 parts by weight or volume of the nitrogen containing compound which, if a solid, had been preheated into liquid form. The resulting solution is then used for plating. During plating the solution may be gently heated to maintain it in liquid form.

Where oxides, hydroxides, carbonates and salts other than halides of the aforementioned metals are used in the preparation of the complex one mole thereof is treated at room temperature with one mole of either hydrobromic or hydroiodic acid' with stirring for a few minutes until a solution is formed. At this time one mole in excess of the nitrogen containing compound is added with stirring followed by the addition of 0.5-1.0 mole of either hydrobromic or hydroiodic acid with or without the addition of a small amount of water. After stirring for a few minutes, usually 5-10 minutes, one part by weight of the resulting solution of the complex is then added to 14 parts by weight of either water or of the nitrogen containing compound which may be the same as initially employed or any one or a mixture of the above enumerated compounds.

In the case of silver, instead of employing either one of the individual halides such as chloride, bromide or iodide to form the silver complex, I have found that a mixture of silver bromide and silver iodide gives excellent deposits of metallic silver. The ratio of silver bromide to silver iodide is immaterial so long as the mixture constitutes one mole of the silver salts.

The following examples will illustrate the preparation of the complexes and their use in plating the various metallic surfaces. It is to be clearly understood that these examples are merely illustrative and are not to be construed as being limitative. All parts given are by weight unless otherwise stated:

Example I 20 grams of silver bromide were first treated with 20 ml. of dimethyl formamide, enough to cover the solid. Then was added 20 ml. of 48% hydrobromic acid. After stirring a short while the volume was made up to 100 ml. with dimethyl formamide.

Example II 15 grams of silver iodide was first treated with 15 ml. of N-methyl-Z-pyrrolidone to cover all of the solid. 25 cc. of .48% hydrobromic acid was slowly added. After stirring awhile 'a paste was formed which was diluted to 100 ml. with N-methyl-Z-pyrrolidone and stirred until dissolved.

Example III 15 grams of silver bromide was mixed with grams of silver iodide; this was covered with 20 ml. of dimethyl acetamide. After stirring a few minutes, 20 ml. of 48% hydrobromic acid was added and stirred a few minutes. Enough dimethyl acetamide was added to bring the volume to 100 ml. with stirring until dissolved.

Example IV To 50 mg. of sodium gold chloride was added 0.5 ml. of dimethyl propionamide. After stirring for one minute 1 ml. of hydroiodic acid (58.7%) was added and stirring continued for an additional minute. 3 ml. of dimethyl propionamide was added and after two minutes of stirring the solution was ready for the plating process. Gold was deposited from this solution on copper and on silver at about 88 F. (31 C.). The presence of a small amount of chromium ion in the plating solution enhances and accelerates the gold plating.

Example V To 50 mg. of palladium chloride was added 0.5 ml. of dimethyl butyramide. 0.5 cc. of 48% hydrobromic acid was added, solution occurred almost immediately. After a few minutes of stirring, 3 cc. of dimethyl butyramide was added and stirred for a few minutes. The plating of copper and stainless steel was carried out at a temperature of 6570 C. yielding a shiny coat on both metals.

Example VI To 0.2 gram of tellurium oxide was added 2.0 cc. of 48% hydrobromic acid. Upon stirring for a few minutes solution occurred. At this time cc. of dimethyl formamide was added. After a minute of stirring 10 cc. of

water was added followed by 1 cc. of 48% hydrobromic acid with stirring for 5 minutes. Water was then added in 25 cc. portions until a total volume of 200 cc. was reached.

Example VII To 1 gram of cuprous chloride was added 5 m1. of dimethyl formamide. After a few minutes of stirring, 5 ml. of 48% hydrobromic acid was added. Stirring was continued while the solution of the complex was diluted to 25 ml. with dimethyl formamide.

tained.

4 Example VIII A piece ofcopper without any pretreatment such as degreasing or bufling was placed into the plating solution of Example II for 10 seconds, removed, washed with water and rubbed with sodium bicarbonate to form a shiny silver coating.

ExampleX A piece of copper without any pretreatment such as degreasing or bufling was placed into the plating solution of Example 111 for 10 seconds, removed, washed with water and rubbed with sodium bicarbonate to form a shiny silver coating.

Example XI A piece of yellow brass was placed in the plating solution of Example I for 30 seconds, removed, washed with water and rubbed with sodium bicarbonate to give a shiny silver plate.

Example XII A piece of bronze was placed in the plating solution of Example 11 for 30 seconds, removed, washed with water and rubbed with sodium bicarbonate to give a shiny coating of silver.

Example XIII Example IV was repeated with the exception that dimethyl propionamide was replaced by an equivalent amount of N-dimethyl aniline and the same results 0b- Example XIV Example V was repeated three times with the exception that dimethyl butyramide was replaced by an equivalent amount of dibutyl amine, tributyl amine and pyridine, respectively, with the same results.

Example X V' A small flat piece of aluminum A by 1 /2" and %4" thick was placed in the plating solution of Example VII and heated on a steam bath for 2 minutes, removed, washed with water and rubbed with sodium bicarbonate to form a shiny copper coating.

The various individual complexes prepared as above are compatible with each other and deposit an alternate layer of metals on the metallic surface being plated. For example, equal parts of the gold and silver complexes when mixed together and a piece of copper placed into the mixture, a layer of silver and gold is deposited on the copper surface within a few minutes. It appears that the silver plates the copper first and the gold then deposits on the silver.

It is to be noted that the presence of a small amount of chromium ion also enhances and accelerates the plating of gold on silver as well as on copper. Any metal coated with copper can then be plated with gold, palladium or silver. Any metal plated with silver can then be plated with gold or palladium.

Iclaim:

1. The process of depositing a metallic coat on a metallic surface without resorting to an electric current which comprises contacting said surface with a solution of a coating complex obtained by dissolving one mole of a compound containing a cation selected from the class consisting of copper, gold, palladium, platinum, silver and tellurium in one mole in excess of at least one nitrogen containing compound selected from the group consisting of compounds having the following general formulae:

( HzC-OH2 N r r R1CON and 2)3 wherein R and R represent a member selected from the group consisting of hydrogen and alkyl group of from 1 to 4 carbon atoms and R and R represent an alkyl group of from 1 to 4 carbon atoms, and in one mole of an acid selected from the class consisting of hydrobromic and hydroiodic.

2. The process according to claim 1 wherein the cation is silver.

3. The process according to claim 1 wherein the cation is palladium.

4. The process according to claim 1 wherein the cation is tellurium.

5. The process according to claim 1 wherein the cation is copper.

6. The process according to claim 1 wherein the cation is gold.

References Cited by the Examiner UNITED STATES PATENTS 3,250,784 5/1966 Gensheimer et a1. 117130 X ALFRED L. LEAVITT, Primary Examiner.

R. S. KENDALL, Assistant Examiner.

Disclaimer 3,294,578.Stanley P. Popeck, Nimmonsburg, N.Y. DEPOSITION OF A ME- TALLIC COAT ON METAL SURFACES. Patent dated Dec. 27, 1966. Disclaimer filed Sept. 30, 1982, by the assignee, Eastman Kodak Co.

Hereby enters this disclaimer to all claims of said patent.

[Official Gazette February 8, 1983.]

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3250784 *Dec 23, 1963May 10, 1966Gen Aniline & Film CorpPyrrolidonyl-gamma-butyramide and process of preparing
Referenced by
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US3472665 *Jun 2, 1967Oct 14, 1969Dow Chemical CoElectroless coating of cobalt and nickel
US3630768 *Jun 28, 1966Dec 28, 1971Electronor CorpChemical deposition formation of anodes
US3917885 *Apr 26, 1974Nov 4, 1975Engelhard Min & ChemElectroless gold plating process
US4241105 *Dec 17, 1979Dec 23, 1980Western Electric Company, Inc.Method of plating the surface of a substrate
US4798626 *Sep 30, 1986Jan 17, 1989Lamerie, N.V.Solutions and creams for silver plating and polishing
US4832743 *Dec 19, 1986May 23, 1989Lamerie, N.V.Gold plating solutions, creams and baths
US4925491 *Mar 10, 1987May 15, 1990Lamerie, N.V.Aqueous solution of silver lactate or acetate
US4975159 *Oct 24, 1989Dec 4, 1990Schering AktiengesellschaftCopper salt, inorganic acid and alkoxylated lactam; reinforcing electroconductivity of printed circuit
US5384154 *May 4, 1994Jan 24, 1995U.S. Philips CorporationEfficiency, simplification
US5955141 *Sep 17, 1997Sep 21, 1999Alpha Metals, Inc.Contacting surface of metal having electropositivity less than silver with aqueous composition comprising silver ions and complexing agent
US6395329 *Sep 29, 1997May 28, 2002Soutar Andrew McintoshPrinted circuit board manufacture
US6860925Apr 8, 2002Mar 1, 2005Enthone IncorporatedFor tarnish-resistant and solderable coating
US6869637 *Sep 21, 2001Mar 22, 2005Atotech Deutschland GmbhCopper inhibitors additionally permit to positively influence the appearance of the surface by leveling the layer of copper that had been roughened by the etching process
US7767009 *Sep 14, 2005Aug 3, 2010OMG Electronic Chemicals, Inc.A silver deposit solution comprisingan acid,a source of silver ions andan additive selected from the group consisting of pyrroles, triazoles, tetrazoles, and mixtures ; including 1,2,3-benzotriazin-4(3H)-one; cost efficiency; simplification
US8110252Aug 3, 2010Feb 7, 2012Omg Electronic Chemicals, LlcSolution and process for improving the solderability of a metal surface
US8349393Jul 29, 2004Jan 8, 2013Enthone Inc.Silver plating in electronics manufacture
DE2633811A1 *Jul 28, 1976Feb 2, 1978Bayer AgKatalysator und verfahren zur herstellung von nitrodiphenylaminen
DE3219665A1 *May 26, 1982Dec 16, 1982Hooker Chemicals Plastics CorpBad fuer die stromlose abscheidung von gold und verfahren zur abscheidung von gold auf einem substrat unter verwendung dieses bades
DE10050862A1 *Oct 6, 2000Apr 25, 2002Atotech Deutschland GmbhBad und Verfahren zum stromlosen Abscheiden von Silber auf Metalloberflächen
DE10050862C2 *Oct 6, 2000Aug 1, 2002Atotech Deutschland GmbhBad und Verfahren zum stromlosen Abscheiden von Silber auf Metalloberflächen
EP0081183A1 *Nov 30, 1982Jun 15, 1983Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V.Process for the electroless depositing of noble metal layers on the surfaces of non-noble metals
EP0107801A1 *Sep 28, 1983May 9, 1984Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V.Process for electroless plating of metal surfaces with layers of metal
EP0785297A2 *Mar 19, 1990Jul 23, 1997ATOTECH Deutschland GmbHAn aqueous acid bath for the electrodeposition of a shiny and tear-free copper coating and its application
WO1996017974A1 *Dec 11, 1995Jun 13, 1996Alpha Fry LtdSilver plating
WO2002029132A1 *Sep 21, 2001Apr 11, 2002Atotech Deutschland GmbhBath and method of electroless plating of silver on metal surfaces
WO2003104527A1 *May 27, 2003Dec 18, 2003Atotech Deutschland GmbhAcidic solution for silver deposition and method for silver layer deposition on metal surfaces
Classifications
U.S. Classification427/437, 106/1.26, 106/1.28, 106/1.5
International ClassificationC23C18/16, C23C18/31, C23C18/42
Cooperative ClassificationC23C18/16, C23C18/42
European ClassificationC23C18/42, C23C18/16
Legal Events
DateCodeEventDescription
Sep 30, 1982ASAssignment
Owner name: EASTMAN KODAK COMPANY, 343 STATE ST. ROCHESTER, N.
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:GAF CORPORATION;REEL/FRAME:004049/0808
Effective date: 19820910