US2956900A - Nickel coating composition and method of coating - Google Patents

Nickel coating composition and method of coating Download PDF

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Publication number
US2956900A
US2956900A US750870A US75087058A US2956900A US 2956900 A US2956900 A US 2956900A US 750870 A US750870 A US 750870A US 75087058 A US75087058 A US 75087058A US 2956900 A US2956900 A US 2956900A
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Prior art keywords
nickel
coating
solution
citric acid
solutions
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US750870A
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Arthur M Carlson
Carl E Prymula
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ALPHA METAL LAB Inc
ALPHA METAL LABORATORIES Inc
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ALPHA METAL LAB Inc
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Priority to US750870A priority Critical patent/US2956900A/en
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/31Coating with metals
    • C23C18/32Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites

Definitions

  • the invention relates to coating surfaces with nickel and more particularly relates to a process of spray metallizing conductors and non-conductors with chemically reduced nickel.
  • An object of this invention is to provide a simple and inexpensive process of providing a smooth, uniform coating of nickel.
  • NiSO -6H O nickel sulphate
  • citric acid in a molar ratio of nickel sulphate to citric acid of between approximately 1.3 to 2.0 in conjunction with a reducer solution in such a manner that the solutions converge on the article to be coated.
  • nickel chloride or nickel formate in place of nickel sulphate, there can be used nickel chloride or nickel formate, in a molar ratio of such salts to citric acid of 1.3 to 2.85.
  • NiSo -6H O nickel sulphate
  • citric acid between 8 to 12 grams per liter
  • the molar ratios of nickel sulphate (NiSO -6H O) to citric acid being as stated above, i.e., 1.3 to 2.0.
  • compositions can, of course, be sold in much more concentrated solutions, or even in a dry state and then diluted with water to make them suitable for the process of this invention.
  • the temperature of the solutions during processing can be varied widely.
  • the temperature limit of the reducer solution is about 140 F., as above this temperature it starts to decompose.
  • Suitable temperatures areap proximately 70 F. to
  • liter-of aqueous solution preferably containing .5- to 2 grams per liter of sodium lauryl sulphate, or other fatty alcohol sulphate.
  • the one gallon of metal solution is diluted to 20 gallons for spraying.
  • the dry reducer mixture is also dissolved in water to give 20 gallons of solution.
  • nickel metal coating for electrolizing we spray the above solutions separately at F. at 12 p.s.i. for approximately 5 minutes on a Vinylite mold, backed by a cool metal plate to conduct away the heat.
  • the article can be coated by dipping into a solution formed by mixing the nickel solution and reducer solutions, agitating the solutions, and then removing the coated article. This procedure is not as fast and does not give a coating which is quite as uniform as the spray process.
  • a process of coating a surface with nickel which comprises spraying separately and directing toward the surface so that the solutions converge on the surface a nickel solution and reducer solution, said nickel solution consisting essentially of a nickel salt, selected from the group consisting of nickel sulphate, nickel chloride, and
  • the results are nickel formate; water, and" citric acid in a molar ratio of nickel sulphate to citric acid of between approximately 1.3 and 2.0, and a molar ratio of such other nickel salts to citric acid. of between. approximately 1.3
  • said reducer solution consisting essentially of an alkaline solution of sodium hydrosulphite and sodium hypophosphite, the molar ratio of sodium hydrosulphite to sodium hypophosphite being between approxi- V mately 1.40 and 3.53.

Description

Oct. 18, 1960 A. M. CARLSON EI'AL ,9
NICKEL COATING COMPOSITION AND METHOD OF COATING spear N SPRHY GUN .JoLuT/aN A LEVELS THNK WITH METHL 50L UTIUN rmwr w/rn J REDUCER sauna/v CR) filfi PRESSURE nsaamrok TO HIR SUPPLY dart ffrym vla.
United States lice NICKEL COATING COMPOSITION AND METHOD or COATING e Arthur M. Carlson, Chicago, and Carl E. Prymula, Zion,
Ill., assignors to Alpha Metal Laboratories, Inc., Chicago, Ill., a corporation of Illinois Filed July 25, 1958,'Ser. No. 750,870
4 Claims. (Cl. 117-47) I The invention relates to coating surfaces with nickel and more particularly relates to a process of spray metallizing conductors and non-conductors with chemically reduced nickel.
An object of this invention is to provide a simple and inexpensive process of providing a smooth, uniform coating of nickel.
These and other objects and advantages are accomplished by spraying an aqueous solution of nickel sulphate (preferably the hydrated nickel sulphate, NiSO -6H O) containing citric acid in a molar ratio of nickel sulphate to citric acid of between approximately 1.3 to 2.0 in conjunction with a reducer solution in such a manner that the solutions converge on the article to be coated.
in place of nickel sulphate, there can be used nickel chloride or nickel formate, in a molar ratio of such salts to citric acid of 1.3 to 2.85.
The reducer solution which we have found to give the most satisfactory results with the above mentioned nickel solutions is as follows:
Grams per liter of aqueous solution Sodium hydroxide 2 to 10 Sodium hydrosulphite 20 to 80 Sodium hypophosphite 5 to 30 Table I Ratio: Thickness, mils. 3.18 0.008 2.00 0.040 1.77 0.042 1.60 0.048 1.32 0.033 1.06 0.00 0.80 0.00
We obtained satisfactory results with concentrations of nickel sulphate (NiSo -6H O) of from 15 to 20 grams per liter and citric acid of between 8 to 12 grams per liter, the molar ratios of nickel sulphate (NiSO -6H O) to citric acid being as stated above, i.e., 1.3 to 2.0.
The above compositions can, of course, be sold in much more concentrated solutions, or even in a dry state and then diluted with water to make them suitable for the process of this invention.
The temperature of the solutions during processing can be varied widely. However, the temperature limit of the reducer solution is about 140 F., as above this temperature it starts to decompose. Suitable temperatures areap proximately 70 F. to
tions, and 70 F. to 180 F.-for the metal solutions.
For cold spraying of plastics, that is, tempcratures of 60 F.i to F.,'we obtain preferred results bysensitizing the plastic surface with 2 to 10 grams of SnCl: per
liter-of aqueous solution, preferably containing .5- to 2 grams per liter of sodium lauryl sulphate, or other fatty alcohol sulphate.
also preferably containing .5 to 2 grams per. liter of sodium lauryl sulphate or other fatty alcohol sulphate; then without rinsing, the plastic is sprayed with the n ckel Metal solution:
NiSO -6H O 3 lb., 5.5 oz. Citric acid -s 1 1b., 11 oz. Water to make 1 gallon.
Reducer mixture:
NaOH 1 lb., 5.5 oz. Na,S O 11 lb., 11.5 oz. NaHz oz 1 1b., OZ-
The one gallon of metal solution is diluted to 20 gallons for spraying. The dry reducer mixture is also dissolved in water to give 20 gallons of solution.
As a specific example of nickel metal coating for electrolizing, we spray the above solutions separately at F. at 12 p.s.i. for approximately 5 minutes on a Vinylite mold, backed by a cool metal plate to conduct away the heat.
We have obtained satisfactory results on copper, aluminum, stainless steel, steel, brass, and plastics. So far as we know, all types of articles can be nickel coated with our solutions.
Instead of using a spray process, the article can be coated by dipping into a solution formed by mixing the nickel solution and reducer solutions, agitating the solutions, and then removing the coated article. This procedure is not as fast and does not give a coating which is quite as uniform as the spray process.
In order to facilitate ready comprehension of this invention and certain aspects of the method and means included within the purview of the same, a non-limiting example of apparatus or applying device useful for practising some of the principles of the invention is illustrated in the accompanying drawing.
While we have disclosed certain preferred embodiments of our invention, many modifications thereto may be made without departing from the spirit of the invention; and we do not wish to be limited to the detailed examples, formulas, and proportions of ingredients set forth, but desire to avail ourselves of all changes within the scope of the appended claims.
We claim:
1. A process of coating a surface with nickel which comprises spraying separately and directing toward the surface so that the solutions converge on the surface a nickel solution and reducer solution, said nickel solution consisting essentially of a nickel salt, selected from the group consisting of nickel sulphate, nickel chloride, and
, Patented o r. 18,1960,
140 F. for reducer sblui The plastic is then rinsed with to 10 grams of. silver nitrate per liter of aqueous SOlllilOIh.
hot spraying of plastics, the results are nickel formate; water, and" citric acid in a molar ratio of nickel sulphate to citric acid of between approximately 1.3 and 2.0, and a molar ratio of such other nickel salts to citric acid. of between. approximately 1.3
and 2.85' and said reducer solution consisting essentially of an alkaline solution of sodium hydrosulphite and sodium hypophosphite, the molar ratio of sodium hydrosulphite to sodium hypophosphite being between approxi- V mately 1.40 and 3.53.
'2. The process of claim 1, wherein the metal solution 10 coating and the temperature of the solutions is from 60 F. to 100 F.
References Cited in the file of this patent UNITED STATES PATENTS 2,689,191 PC5881 Sept. 14, 1954 FOREIGN PATENTS 493,379 Great Britain Oct. 25, 1938 OTHER REFERENCES Brenner et al.: Partof the Journal of Research of the National Bureau of Standards, Research Paper RP. 1835, vol. 39, November 1947, pp. 385-395.
15 Chakraborty et al.: J. Sci. Ind. Research (India) 138,
433-40 (1954), CA 49: 2808b.
Myers: Z. Anorg Chem. 80, pp. 93-103, CA 7: 21689.

Claims (2)

1. A PROCESS OF COATING A SURFACE WITH NICKEL WHICH COMPRISES SPRAYING SEPARATELY AND DIRECTING TOWARD THE SURFACE SO THAT THE SOLUTIONS CONVERGE ON THE SURFACE A NICKEL SOLUTION AND REDUCER SOLUTION, SAID NICKEL SOLUTION CONSISTING ESSENTIALLY OF A NICKEL SALT, SELECTED FROM THE GROUP CONSISTING OF NICKEL SULPHATE, NICKEL CHLORIDE, AND NICKEL FORMATE, WATER, AND CITRIC ACID IN A MOLAR RATIO OF NICKEL SULPHATE TO CITRIC ACID OF BETWEEN APPROXIMATELY 1.3 AND 2.0, AND A MOLAR RATIO OF SUCH OTHER NICKEL SALTS TO CITRIC ACID OF BETWEEN APPROXIMATELY 1.3 AND 2.85 AND SAID REDUCER SOLUTION CONSISTING ESSENTIALLY OF AN ALKALINE SOLUTION OF SODIUM HYDROSULPHITE AND SODIUM HYPOPHOSPHITE, THE MOLAR RATIO OF SODIUM HYDROSULPHITE TO SODIUM HYPOPHOSPHITE BEING BETWEEN APPROXIMATELY 1.40 AND 3.53.
4. THE PROCESS OF CLAIM 1, WHEREIN THE SURFACE IS AN ORGANIC PLASTIC SENSITIZED WITH STANNOUS CHLORIDE PRIOR TO COATING AND THE TEMPERATURE OF THE SOLUTIONS IS FROM 60* F. TO 100*F.
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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3252949A (en) * 1960-12-30 1966-05-24 Monsanto Co Syndiotactic oil-soluble methacrylate polymers
US3357854A (en) * 1964-10-30 1967-12-12 Darrell D Hays Nickel plating process
DE1281768B (en) * 1963-09-30 1968-10-31 Teldec Telefunken Decca Process for electroless metallization of lacquer foils for record production
US3967010A (en) * 1973-11-30 1976-06-29 Kuraray Co., Ltd. Process for the production of metal-plated staple fibers
US4170461A (en) * 1976-12-29 1979-10-09 Ppg Industries, Inc. Heat treatment of electrolessly deposited cuprous oxide coating
US4190503A (en) * 1977-12-28 1980-02-26 Sony Corporation Method of manufactureing a record matrix
US4262044A (en) * 1980-05-16 1981-04-14 Kuczma Jr John J Method for the electroless nickel plating of long bodies
US4278477A (en) * 1980-03-19 1981-07-14 Amchem Products, Inc. Metal treatment
US4315055A (en) * 1976-12-29 1982-02-09 Ppg Industries, Inc. Direct electroless deposition of cuprous oxide films
US4368223A (en) * 1981-06-01 1983-01-11 Asahi Glass Company, Ltd. Process for preparing nickel layer
US4400436A (en) * 1980-06-30 1983-08-23 Ppg Industries, Inc. Direct electroless deposition of cuprous oxide films
US4609575A (en) * 1984-07-02 1986-09-02 Fsi Corporation Method of apparatus for applying chemicals to substrates in an acid processing system
US4766009A (en) * 1984-07-23 1988-08-23 Hitachi, Ltd. Selective working method
US4837046A (en) * 1986-08-08 1989-06-06 Nippon Paint Co., Ltd. Method for forming ferrite film
US5863603A (en) * 1993-04-14 1999-01-26 Micron Technology, Inc. Liquid vapor deposition or etching method
US6065424A (en) * 1995-12-19 2000-05-23 Cornell Research Foundation, Inc. Electroless deposition of metal films with spray processor

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB493379A (en) * 1937-04-07 1938-10-07 Etienne Challet Electric kitchen stove or oven
US2689191A (en) * 1948-12-10 1954-09-14 Rca Corp Formation of reflecting coatings

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB493379A (en) * 1937-04-07 1938-10-07 Etienne Challet Electric kitchen stove or oven
US2689191A (en) * 1948-12-10 1954-09-14 Rca Corp Formation of reflecting coatings

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3252949A (en) * 1960-12-30 1966-05-24 Monsanto Co Syndiotactic oil-soluble methacrylate polymers
DE1281768B (en) * 1963-09-30 1968-10-31 Teldec Telefunken Decca Process for electroless metallization of lacquer foils for record production
US3357854A (en) * 1964-10-30 1967-12-12 Darrell D Hays Nickel plating process
US3967010A (en) * 1973-11-30 1976-06-29 Kuraray Co., Ltd. Process for the production of metal-plated staple fibers
US4170461A (en) * 1976-12-29 1979-10-09 Ppg Industries, Inc. Heat treatment of electrolessly deposited cuprous oxide coating
US4315055A (en) * 1976-12-29 1982-02-09 Ppg Industries, Inc. Direct electroless deposition of cuprous oxide films
US4190503A (en) * 1977-12-28 1980-02-26 Sony Corporation Method of manufactureing a record matrix
US4278477A (en) * 1980-03-19 1981-07-14 Amchem Products, Inc. Metal treatment
WO1981003343A1 (en) * 1980-05-16 1981-11-26 J Kuczma Method for the electroless nickel plating of long bodies
US4262044A (en) * 1980-05-16 1981-04-14 Kuczma Jr John J Method for the electroless nickel plating of long bodies
US4400436A (en) * 1980-06-30 1983-08-23 Ppg Industries, Inc. Direct electroless deposition of cuprous oxide films
US4368223A (en) * 1981-06-01 1983-01-11 Asahi Glass Company, Ltd. Process for preparing nickel layer
US4609575A (en) * 1984-07-02 1986-09-02 Fsi Corporation Method of apparatus for applying chemicals to substrates in an acid processing system
US4766009A (en) * 1984-07-23 1988-08-23 Hitachi, Ltd. Selective working method
US4837046A (en) * 1986-08-08 1989-06-06 Nippon Paint Co., Ltd. Method for forming ferrite film
US5863603A (en) * 1993-04-14 1999-01-26 Micron Technology, Inc. Liquid vapor deposition or etching method
US6065424A (en) * 1995-12-19 2000-05-23 Cornell Research Foundation, Inc. Electroless deposition of metal films with spray processor

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