US2472393A - Process and bath for copper coating ferrous metal - Google Patents

Process and bath for copper coating ferrous metal Download PDF

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Publication number
US2472393A
US2472393A US555762A US55576244A US2472393A US 2472393 A US2472393 A US 2472393A US 555762 A US555762 A US 555762A US 55576244 A US55576244 A US 55576244A US 2472393 A US2472393 A US 2472393A
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chloride
copper
bath
cuprous chloride
cuprous
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US555762A
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Samuel C Avallone
Arch W Harris
Esther J Whiting
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American Steel and Wire Company of New Jersey
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American Steel and Wire Company of New Jersey
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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
    • C23C18/38—Coating with copper

Definitions

  • the present invention relates to a method of coating with a lubricating medium, ferrousmetals such as ordinary carbon steels and alloys thereof such as the stainless steels consisting of combinations of nickel and chromium or chromium alone, the purpose being to furnish a lubricating medium, in the form of a coating, on wire or strip, made from the aforementioned ferrous metals, which is to be subjected to cold forming operations such as wire drawing, stamping, cold heading, etc.
  • ferrousmetals such as ordinary carbon steels and alloys thereof such as the stainless steels consisting of combinations of nickel and chromium or chromium alone
  • the invention pertains to a method of chemically coating stainless steel wires and rods with copper as a lubricating medium, whereby the rods and wire can be cold drawn without necessitating coating the same with lead, which is expensive and by no means entirely satisfactory when working with the finer gages of wire. It has been established in practice that rods or,wire coated with copper, when the coating has been-applied in the manner of this invention, can be given just as heavy reductions and drawn just as fast as is possible when lead coatings are employed and yet cost considerably less as compared with the use of lead coatings.
  • the copper coating is applied to the stainless steel or ordinary carbon steel wire being drawn by simply immersing the wire in a suitable aqueous bath containing, by weight, approximately 1.25% cuprous chloride, 1.25% ammonium chloride, 3.0% hydrochloric acid, 0.01% Carbowax #4000, the balance being water.
  • a suitable aqueous bath containing, by weight, approximately 1.25% cuprous chloride, 1.25% ammonium chloride, 3.0% hydrochloric acid, 0.01% Carbowax #4000, the balance being water.
  • Metallic tin or stannous chloride can also be used to maintain the cuprous chloride in a reduced condition.
  • the bath can be operated in the range between 70 F. and 195 F" t3; preferable range being between 180 F. and 1 F.
  • the metal surfaces to be coated with copper by this invention must be chemically clean, that is, free of all extraneous matter, such as oxides, grease, etc., and at the same time not be passive so as to hinder the proper chemical reactions taking place between the coating bath and base metal to be coated.
  • the cuprous chloride 2 is insoluble in water, but is soluble in an aqueous solution of ammonium chloride and hydrochloric acid. Any salt such as sodium chloride, calcium chloride, potassium chloride which will raise the solubility of the cuprous chloride in an aqueous solution can be substituted for the ammonium chloride.
  • the scrap copper, metallic tin or stannous chloride are used to keep the cuprous chloride in the reduced or "ous condition.
  • the Carbowax is an additive agent which serves to produce a fine grain copper deposit which makes it possible to deposit a greater amount of copper and at the same time obtain an adherent coating on ferrous metals and their alloys such as V the stainless steels.
  • the above bath can have its composition varied to a certain degree, that is, the ammonium chloride content can be varied from 0.4% to 20%, the cuprous chloride from 0.40% to 10%, and the hydrochloric acid from 2.0% to 12% with suflicient stannous chloride, metallic tin or scrap cop-' per added thereto to keep the cuprous chloride in a reduced state.
  • Alsoaddition agents such as triethanolamine napthanate and commercial wheat flour can also be used instead of Carbowax, Carbowax being a registered trade mark of Carbide and Carbon Chemicals Company, New York, N.
  • Carbowax #4000 being composed of higher polyethylene glycols having an average molecular weight ranging from 3500# to 4500# determined by acetylation, "Carbowax #4000 thereby being a grade of the composition marketed under the trade mark "Carbowax. Any addition agent which would produce a fine grained copper deposit in conjunction with this bath could be used successfully. Approximately 1% of flour is used or between .01% and 0.2% Carbowax.
  • the present invention makes it possible to deposit a. relatively heavy coat of fine grained copper on stainless steels such as 18-8 (18% chromium-8% nickel) and the straight chromium types while even heavier fine grained adherent copper coatings can be applied to the ordinary straight carbon steels. It is found in practice that much heavier coatings of copper are capable of being applied to ordinary carbon steels than has been possible when using old prior art methods. The coatings though being many times heavier are fine grained and completely adherent to the ferrous base metal.
  • the method described herein is very flexible in operation in that it lends itself to either continuous or batch type treatment and is more economical to use because it is not necessary to apply any electrolytic means thereto inasmuch as the method is one involving only straight chemical deposition.
  • the method of chemically depositing fine grain copper coating on ferrous metal comprising immersing the metal in an aqueous bath consisting by weight of 0.40 to 20% cuprous chloride, 2 to 12% hydrochloric acid, 0.4 to 20% of an agent for enhancing solubility of cuprous chloride selected from the grou consisting of ammonium chloride, sodium chloride, calcium chloride and potassium chloride, and the remainder water, the bath being maintained at a temperature in the range 70 to 195 F. and in the presence of a reducing agent for preventing oxidation of cuprous chloride, the reducing agent being of the group consisting of metallic copper, metallic tin and stannous chloride.
  • the method of chemically depositing fine grain copper coating on ferrous metal as lubricant for cold working the metal comprising immersing the metal in an aqueous bath consisting by weight of 0.40 to 10% cuprous chloride, 2 to 12% hydrochloric acid, 0.4 to of an agent for enhancing solubility of cuprous chloride selected from the group consisting of ammonium chloride, sodium chloride, calcium chloride and potassium chloride, 0.01 to 0.20% polyethylene glycol of molecular weight 3500 to 4500, and the remainder water.
  • the bath being maintained at a temperature in the range 70 to 195 F. and in the presence of a reducing agent for preventing oxidation of cuprous chloride, the reducing agent being of the group consisting of metallic copper,
  • the method of chemically depositing fine 4 bath being maintained at a temperature to F. and in the presence of a reducing agent for preventing oxidation of cuprous chloride, the reducing agent being of the group consisting of fietailic copper, metallic tin and stannous chlo- 4.
  • an aqueous solution consisting by weight of 0.40 to 10% cuprous chloride, 2 to 12% hydrochloric acid, 0.4 to 20% of an agent for enhancing solubility of cuprous chloride selected from the group consisting of ammonium chloride, sodium chloride, calcium chloride and potassium chloride, and the remainder water, the solution being in the presence of a reducing agent for preventing oxidation of cuprous chloride, the reducing agent being of the group consisting of figtallic copper, metallic tin and stannous chlo- 5.
  • an aqueous solution consisting by weight of 0.40 to 10% cuprous chloride, 2 to 12% hydrochloric acid, 0.4 to 20% of an agent for enhancing solubility of cuprous chloride selected from the group consisting of ammonium chloride, sodium chloride, calcium chloride, and potassium chloride, 0.01 to 0.20% polyethylene glycol of molecular weight 3500 to 4500, and the remainder water, the solution being in the presence of a reducing agent for preventing oxidation of cuprous chloride, the reducing agent being of the group consisting of metallic copper, metallic tin and stannous chloride.
  • an aqueous solution consisting by weight of approximately 1.25% cuprous chloride, 3.0% hydrochloric acid, 1.25% ammonium chloride, 0.01% polyethylene glycol of molecular weight 3500 to 4500, and the remainder water, the solution being in the presence of a reducing agent for preventing oxidation of cuprous chloride, the reducing agent. being of the group consisting of metallic copper, metallic tin and stannous chloride.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Description

Patented June 7, 1949 PROCESS AND BATH FOR COPPER COATING FERROUS METAL Samuel C. Avallone, Cleveland Heights, and Arch W. Harris and Esther J. Whiting, Cleveland, Ohio, assignors to The American Steel and Wire Company of New Jersey, a corporation of New Jersey No Drawing. Application September 25, 1944, Serial No. 555,762
6 Claims. (Cl. 117-130) The present invention relates to a method of coating with a lubricating medium, ferrousmetals such as ordinary carbon steels and alloys thereof such as the stainless steels consisting of combinations of nickel and chromium or chromium alone, the purpose being to furnish a lubricating medium, in the form of a coating, on wire or strip, made from the aforementioned ferrous metals, which is to be subjected to cold forming operations such as wire drawing, stamping, cold heading, etc.
More specifically, for example, the invention pertains to a method of chemically coating stainless steel wires and rods with copper as a lubricating medium, whereby the rods and wire can be cold drawn without necessitating coating the same with lead, which is expensive and by no means entirely satisfactory when working with the finer gages of wire. It has been established in practice that rods or,wire coated with copper, when the coating has been-applied in the manner of this invention, can be given just as heavy reductions and drawn just as fast as is possible when lead coatings are employed and yet cost considerably less as compared with the use of lead coatings.
In accordance with the present invention, the copper coating is applied to the stainless steel or ordinary carbon steel wire being drawn by simply immersing the wire in a suitable aqueous bath containing, by weight, approximately 1.25% cuprous chloride, 1.25% ammonium chloride, 3.0% hydrochloric acid, 0.01% Carbowax #4000, the balance being water. In order to maintain the cuprous chloride in the reduced condition it is necessary to have scrap copper present in the bath. Metallic tin or stannous chloride can also be used to maintain the cuprous chloride in a reduced condition. The bath can be operated in the range between 70 F. and 195 F" t3; preferable range being between 180 F. and 1 F.
It is understood, of course, that the metal surfaces to be coated with copper by this invention must be chemically clean, that is, free of all extraneous matter, such as oxides, grease, etc., and at the same time not be passive so as to hinder the proper chemical reactions taking place between the coating bath and base metal to be coated.
The success of the above bath in plating copper onto ferrous metals and their alloys, such as 'the stainless steels, depends on getting the cuprous chloride in solution and thereafter keeping it in the reduced state. The cuprous chloride 2 is insoluble in water, but is soluble in an aqueous solution of ammonium chloride and hydrochloric acid. Any salt such as sodium chloride, calcium chloride, potassium chloride which will raise the solubility of the cuprous chloride in an aqueous solution can be substituted for the ammonium chloride. The scrap copper, metallic tin or stannous chloride are used to keep the cuprous chloride in the reduced or "ous condition. The Carbowax is an additive agent which serves to produce a fine grain copper deposit which makes it possible to deposit a greater amount of copper and at the same time obtain an adherent coating on ferrous metals and their alloys such as V the stainless steels.
The above bath can have its composition varied to a certain degree, that is, the ammonium chloride content can be varied from 0.4% to 20%, the cuprous chloride from 0.40% to 10%, and the hydrochloric acid from 2.0% to 12% with suflicient stannous chloride, metallic tin or scrap cop-' per added thereto to keep the cuprous chloride in a reduced state. Alsoaddition agents such as triethanolamine napthanate and commercial wheat flour can also be used instead of Carbowax, Carbowax being a registered trade mark of Carbide and Carbon Chemicals Company, New York, N. Y., for proprietary, synthetic, nonvolatile, water soluble waxes, Carbowax #4000 being composed of higher polyethylene glycols having an average molecular weight ranging from 3500# to 4500# determined by acetylation, "Carbowax #4000 thereby being a grade of the composition marketed under the trade mark "Carbowax. Any addition agent which would produce a fine grained copper deposit in conjunction with this bath could be used successfully. Approximately 1% of flour is used or between .01% and 0.2% Carbowax.
It has also been foundthat a bath from which the ammonium chloride has been omitted will function satisfactorily providing the hydrochloric acid content is sufficiently high to afiord the required solubility for the cuprous chloride.
The success of the coating baths described herein depends on keeping the cuprous chloride in the reduced state, and the use of an additive agent which will function in such a manner as to produce a fine grained deposit of copper.
Many efforts have been made heretofore to develop a method for chemically depositing copper on stainless steel, but without any degree of success. The present invention makes it possible to deposit a. relatively heavy coat of fine grained copper on stainless steels such as 18-8 (18% chromium-8% nickel) and the straight chromium types while even heavier fine grained adherent copper coatings can be applied to the ordinary straight carbon steels. It is found in practice that much heavier coatings of copper are capable of being applied to ordinary carbon steels than has been possible when using old prior art methods. The coatings though being many times heavier are fine grained and completely adherent to the ferrous base metal. The method described herein is very flexible in operation in that it lends itself to either continuous or batch type treatment and is more economical to use because it is not necessary to apply any electrolytic means thereto inasmuch as the method is one involving only straight chemical deposition.
We claim:
1. The method of chemically depositing fine grain copper coating on ferrous metal comprising immersing the metal in an aqueous bath consisting by weight of 0.40 to 20% cuprous chloride, 2 to 12% hydrochloric acid, 0.4 to 20% of an agent for enhancing solubility of cuprous chloride selected from the grou consisting of ammonium chloride, sodium chloride, calcium chloride and potassium chloride, and the remainder water, the bath being maintained at a temperature in the range 70 to 195 F. and in the presence of a reducing agent for preventing oxidation of cuprous chloride, the reducing agent being of the group consisting of metallic copper, metallic tin and stannous chloride.
2. The method of chemically depositing fine grain copper coating on ferrous metal as lubricant for cold working the metal comprising immersing the metal in an aqueous bath consisting by weight of 0.40 to 10% cuprous chloride, 2 to 12% hydrochloric acid, 0.4 to of an agent for enhancing solubility of cuprous chloride selected from the group consisting of ammonium chloride, sodium chloride, calcium chloride and potassium chloride, 0.01 to 0.20% polyethylene glycol of molecular weight 3500 to 4500, and the remainder water. the bath being maintained at a temperature in the range 70 to 195 F. and in the presence of a reducing agent for preventing oxidation of cuprous chloride, the reducing agent being of the group consisting of metallic copper,
metallic tin and stannous chloride.
3. The method of chemically depositing fine 4 bath being maintained at a temperature to F. and in the presence of a reducing agent for preventing oxidation of cuprous chloride, the reducing agent being of the group consisting of fietailic copper, metallic tin and stannous chlo- 4. As a bath for chemical deposition of copper on ferrous metals, an aqueous solution consisting by weight of 0.40 to 10% cuprous chloride, 2 to 12% hydrochloric acid, 0.4 to 20% of an agent for enhancing solubility of cuprous chloride selected from the group consisting of ammonium chloride, sodium chloride, calcium chloride and potassium chloride, and the remainder water, the solution being in the presence of a reducing agent for preventing oxidation of cuprous chloride, the reducing agent being of the group consisting of figtallic copper, metallic tin and stannous chlo- 5. As a bath for chemical deposition of copper on ferrous metals, an aqueous solution consisting by weight of 0.40 to 10% cuprous chloride, 2 to 12% hydrochloric acid, 0.4 to 20% of an agent for enhancing solubility of cuprous chloride selected from the group consisting of ammonium chloride, sodium chloride, calcium chloride, and potassium chloride, 0.01 to 0.20% polyethylene glycol of molecular weight 3500 to 4500, and the remainder water, the solution being in the presence of a reducing agent for preventing oxidation of cuprous chloride, the reducing agent being of the group consisting of metallic copper, metallic tin and stannous chloride.
6. As a bath for chemical deposition of copper on ferrous metals, an aqueous solution consisting by weight of approximately 1.25% cuprous chloride, 3.0% hydrochloric acid, 1.25% ammonium chloride, 0.01% polyethylene glycol of molecular weight 3500 to 4500, and the remainder water, the solution being in the presence of a reducing agent for preventing oxidation of cuprous chloride, the reducing agent. being of the group consisting of metallic copper, metallic tin and stannous chloride.
SAMUEL C. AVALLONE. ARCH W. HARRIS. ESTHER J. WHITING.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 1,969,553 Gernes Aug. 7, 1934 2,133,255 Rogers Oct. 11, 1938 2,217,921 Saukaites Oct. 15, 1940
US555762A 1944-09-25 1944-09-25 Process and bath for copper coating ferrous metal Expired - Lifetime US2472393A (en)

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Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2576718A (en) * 1949-01-08 1951-11-27 Fred R Holland Method of testing for the presence of brine in wells
US2655207A (en) * 1949-05-05 1953-10-13 George G Outterson Safety control system for fuel burners
US2664363A (en) * 1953-03-16 1953-12-29 Meth Max Method of depositing copper
US2680711A (en) * 1950-03-10 1954-06-08 Norwitz George Deposition of copper by immersion
US2739915A (en) * 1950-07-20 1956-03-27 Schuster Ludwig Karl Multiple action lubricating composition
US2742412A (en) * 1952-07-05 1956-04-17 Metallic Industry Nv Electrolytic deposition of copper
US2748023A (en) * 1954-11-16 1956-05-29 Meth Max Method and apparatus for depositing copper
US2771380A (en) * 1954-08-02 1956-11-20 Burgess Battery Co Method of plating copper particles with silver
US2872348A (en) * 1946-05-06 1959-02-03 Lowell D Eubank Fused salt method for coating uranium with a metal
US2892801A (en) * 1955-12-13 1959-06-30 Gen Electric Catalysts
US2893544A (en) * 1953-11-12 1959-07-07 Kenneth F Russell Apparatus for drawing wire
US2931760A (en) * 1957-09-25 1960-04-05 Leon R Westbrook Acid copper plating
US3046159A (en) * 1957-12-17 1962-07-24 Hughes Aircraft Co Method of copper plating by chemical reduction
US3141780A (en) * 1962-03-30 1964-07-21 Minnesota Mining & Mfg Copper coating compositions
US3346404A (en) * 1965-01-26 1967-10-10 Amchem Prod Chemical plating process
DE1300762B (en) * 1965-03-23 1969-08-07 W Kampschulte & Cie Dr Alkaline solution and process for depositing copper on non-conductors
US3472664A (en) * 1966-09-15 1969-10-14 Enthone Inhibiting stardusting in electroless copper plating
US3607317A (en) * 1969-02-04 1971-09-21 Photocircuits Corp Ductility promoter and stabilizer for electroless copper plating baths
US3620822A (en) * 1968-11-22 1971-11-16 Hooker Chemical Corp Process of copper plating super-refined steel
US3751289A (en) * 1971-08-20 1973-08-07 M & T Chemicals Inc Method of preparing surfaces for electroplating
US3993491A (en) * 1973-12-07 1976-11-23 Surface Technology, Inc. Electroless plating
US4199623A (en) * 1974-11-01 1980-04-22 Kollmorgen Technologies Corporation Process for sensitizing articles for metallization and resulting articles
US4239538A (en) * 1976-03-30 1980-12-16 Surface Technology, Inc. Catalytic primer
US4259113A (en) * 1976-05-26 1981-03-31 Kollmorgen Technologies Corporation Composition for sensitizing articles for metallization
US4390377A (en) * 1981-01-12 1983-06-28 Hogg James W Novel continuous, high speed method of galvanizing and annealing a continuously travelling low carbon ferrous wire
US4450190A (en) * 1977-05-13 1984-05-22 Kollmorgen Technologies Corporation Process for sensitizing articles for metallization and resulting articles
US4662944A (en) * 1972-07-11 1987-05-05 Kollmorgen Technologies Corporation Process and composition for sensitizing articles for metallization
US4758025A (en) * 1985-06-18 1988-07-19 Mobil Oil Corporation Use of electroless metal coating to prevent galling of threaded tubular joints

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1969553A (en) * 1934-08-07 Electrolyte for the deposition of
US2133255A (en) * 1937-05-19 1938-10-11 Percy A E Armstrong Process of electroplating copper
US2217921A (en) * 1938-03-23 1940-10-15 American Chem Paint Co Art of drawing ferrous metal

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1969553A (en) * 1934-08-07 Electrolyte for the deposition of
US2133255A (en) * 1937-05-19 1938-10-11 Percy A E Armstrong Process of electroplating copper
US2217921A (en) * 1938-03-23 1940-10-15 American Chem Paint Co Art of drawing ferrous metal

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2872348A (en) * 1946-05-06 1959-02-03 Lowell D Eubank Fused salt method for coating uranium with a metal
US2576718A (en) * 1949-01-08 1951-11-27 Fred R Holland Method of testing for the presence of brine in wells
US2655207A (en) * 1949-05-05 1953-10-13 George G Outterson Safety control system for fuel burners
US2680711A (en) * 1950-03-10 1954-06-08 Norwitz George Deposition of copper by immersion
US2739915A (en) * 1950-07-20 1956-03-27 Schuster Ludwig Karl Multiple action lubricating composition
US2742412A (en) * 1952-07-05 1956-04-17 Metallic Industry Nv Electrolytic deposition of copper
US2664363A (en) * 1953-03-16 1953-12-29 Meth Max Method of depositing copper
US2893544A (en) * 1953-11-12 1959-07-07 Kenneth F Russell Apparatus for drawing wire
US2771380A (en) * 1954-08-02 1956-11-20 Burgess Battery Co Method of plating copper particles with silver
US2748023A (en) * 1954-11-16 1956-05-29 Meth Max Method and apparatus for depositing copper
US2892801A (en) * 1955-12-13 1959-06-30 Gen Electric Catalysts
US2931760A (en) * 1957-09-25 1960-04-05 Leon R Westbrook Acid copper plating
US3046159A (en) * 1957-12-17 1962-07-24 Hughes Aircraft Co Method of copper plating by chemical reduction
US3141780A (en) * 1962-03-30 1964-07-21 Minnesota Mining & Mfg Copper coating compositions
US3346404A (en) * 1965-01-26 1967-10-10 Amchem Prod Chemical plating process
DE1300762B (en) * 1965-03-23 1969-08-07 W Kampschulte & Cie Dr Alkaline solution and process for depositing copper on non-conductors
US3472664A (en) * 1966-09-15 1969-10-14 Enthone Inhibiting stardusting in electroless copper plating
US3620822A (en) * 1968-11-22 1971-11-16 Hooker Chemical Corp Process of copper plating super-refined steel
US3607317A (en) * 1969-02-04 1971-09-21 Photocircuits Corp Ductility promoter and stabilizer for electroless copper plating baths
US3751289A (en) * 1971-08-20 1973-08-07 M & T Chemicals Inc Method of preparing surfaces for electroplating
US4662944A (en) * 1972-07-11 1987-05-05 Kollmorgen Technologies Corporation Process and composition for sensitizing articles for metallization
US3993491A (en) * 1973-12-07 1976-11-23 Surface Technology, Inc. Electroless plating
US4199623A (en) * 1974-11-01 1980-04-22 Kollmorgen Technologies Corporation Process for sensitizing articles for metallization and resulting articles
US4239538A (en) * 1976-03-30 1980-12-16 Surface Technology, Inc. Catalytic primer
US4259113A (en) * 1976-05-26 1981-03-31 Kollmorgen Technologies Corporation Composition for sensitizing articles for metallization
US4450190A (en) * 1977-05-13 1984-05-22 Kollmorgen Technologies Corporation Process for sensitizing articles for metallization and resulting articles
US4390377A (en) * 1981-01-12 1983-06-28 Hogg James W Novel continuous, high speed method of galvanizing and annealing a continuously travelling low carbon ferrous wire
US4758025A (en) * 1985-06-18 1988-07-19 Mobil Oil Corporation Use of electroless metal coating to prevent galling of threaded tubular joints

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