US2990296A - Chemical plating of metal-boron alloys - Google Patents

Chemical plating of metal-boron alloys Download PDF

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US2990296A
US2990296A US753192A US75319258A US2990296A US 2990296 A US2990296 A US 2990296A US 753192 A US753192 A US 753192A US 75319258 A US75319258 A US 75319258A US 2990296 A US2990296 A US 2990296A
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metal
plating
percent
solution
boron
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US753192A
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Ralph M Hoke
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Callery Chemical Co
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Callery Chemical Co
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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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9335—Product by special process
    • Y10S428/936—Chemical deposition, e.g. electroless plating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12937—Co- or Ni-base component next to Fe-base component

Definitions

  • This invention relates to a method of chemical plating and more particularly to a method of plating metal objects with metal-boron alloys.
  • Nickel-boron and cobalt-boron alloys are known for their superior flowing properties, wear resistance, and hardness.
  • Metal boron alloys, or metal borides, are particularly useful as coatings for steel and other metals that do not possess these desirable properties.
  • the metalboron alloys are also useful as catalysts for a number of chemical reactions, e.g., hydrogenation reactions. Coatings of metal-boron alloys on other metallic base materials are particularly desirable as catalysts since a maximum amount of catalytic surface is provided by a minimum amount of the metal-boron alloy.
  • This invention is based on my discovery that an aqueous solution of an amine borane, X-BI-l Where X is an amine, and a soluble nickel or cobalt salt is a stable chemical plating solution.
  • a material with a catalytically active surface is contacted with this plating solution, a reaction occurs at the surface forming an adherent continuous plate of metal-boron alloy on the surface.
  • the alloy plate itself is catalytically active so that the surface reaction can be continued to form a plate of any desired thickness.
  • any clean metal surface, free of oxide film is catalytically active. Glass, waxes, e.g. paraifinic waxes, natural fibers, and synthetic organic polymers, e.g. polyethylene and nylon, exhibit essentially no catalytic activity.
  • the solution or plating bath of this invention comprises an aqueous solution containing from about: (1) 0.02 to 6 parts by weight metal ion of the metal boron alloy to be plated, and (2) 0.1 to 3 parts by weight of boraneradical, EH
  • the metal ion i.e. cobalt, or nickel ion
  • any soluble metal salt such as nickel sulfate, nickel chloride, nickel acetate, cobaltoussulfate, cobaltous chloride or other suitable soluble salts.
  • the borane radical is provided by the use of any secondary or tertiary amine borane, e.g. trimethylamine borane, dimethylamine borane, tripropylamine borane, pyridine borane and lutidine borane.
  • Secondary amine boranes are not satisfactory for use in the plating baths because they are rapidly decomposed by hydrolysis reactions.
  • the pH of the plating baths should be maintained below about 6.5; at higher pH values the plating reaction is extremely slow and some metal ion precipitates as the hydroxide. It is preferred to maintain the pH above about 2 because at lower pH values the solution is only metastable and tends to react spontaneously forming a large amount of particulate precipitate so that only a small proportion of the metal-boron alloy is plated.
  • the initial pH of the aqueous plating solutions containing the metal salt and the amine borane are within the preferred range. As the plating reaction proceeds the pH of the solution increases because of the release of amine from the reacted amine borane. If the pH increases to too high a value, the solution can be acidified with any non-oxidizing acid, e.g. HCl. It is particularly convenient to buffer the plating solution with a weak, non-oxidizing acid, e.g. acetic acid or boric acid.
  • the plating baths of this invention have varying degrees of activity; the more active baths plate at a higher rate.
  • the activity of the bath increases with increasing metal 2,990,296 Patented June 27, 1951 p ce 2 ion concentration and increasing borane radical concentration.
  • the activity of the bath also increases with a decrease in pH.
  • the plating bath may be used at any temperature between about room temperature and the boiling point of the solution with the activity of the bath increasing with increasing temperature.
  • the object to be plated is immersed in the plating bath and the plating commences.
  • the object may conveniently be suspended by a string or rope made of-natural or synthetic fiber, or it may be suspended in a cloth or supported by a wood, glass, or synthetic polymer rack. If a metal piece is used to support the object to be plated, some of the bath will be consumed in plating the support. After the object has been plated, it is removed from the bath and washed with water to remove the bath solution and permitted to dry.
  • Metal objects to be plated must have clean surfaces free of oxide film.
  • the objects are cleaned by any of the conventional cleaning procedures.
  • the clean metal surface 'catalyzes the chemical reduction reaction which results in a metal-boron alloy plate on the clean surface.
  • the plating solution in a vessel that exposes only non-active surfaces to the bath.
  • Glass vessels are most convenient, and synthetic polymer vessels, such as polyethylene vessels, and vessels lined with nonactive material may be ued, e.g., paraffin Wax lined, polyethylene lined, or polyvinylidine chloride lined vessels.
  • the plating process is then selective; the plating occurs on the metal object immersed in the solution and does not occur on the vessel walls.
  • metal-boron alloy particulate precipitate When plating has proceeded for several hours, a small amount of metal-boron alloy particulate precipitate is formed and collects at the bottom of the vessel. This precipitate is itself catalytically active so that if it is not removed some of the plating solution will be consumed by reaction induced by the precipitate. The precipitate may be removed by filtration.
  • the chemical plating consumes borane radical and metal ion; any desired concentration or concentration range may be maintained by adding additional amine borane or metal salts to the plating solution.
  • compositions of the solutions are expressed in weight percent of anhydrous reactants.
  • the actual metal salts used were hydrates.
  • Example II A plating solution was prepared which contained 0.95 wt. percent (CH NH-BH 5.14 wt. percent NiCl and 93.91 wt. percent water. The pH of the solution was 5.4. A carbon steel test panel was immersed in the solution maintained at 18 C. for 2 /3 hours. A nickel-boron alloy immediately started to plate on the steel panel. During the course of the plating reaction the pH increased to 6.13
  • the average rate of plate-deposition was-0.019 inches per'hour.
  • Exahiple [II 1:56 ate of fiofmatiori at mm allo plate is incr ased if t li solution ismiiifei'ed to reduce-the? increasedn pH (hiring thecouiseof' the reaction.
  • a buffered solution:contairiing' 3.7 'wt. percent CH NH-BH ,9.3 wt. percenmsic1 wt; percent'H BO and 284.5 wt. percent water had-'apHof tQS.
  • a nickel-boronalloy was pl'ated'z on a" carbonsteel panel immersed in the solutionfo r 6%h ours at" 18 C.
  • the average plating rate was 0.091 X1 0- inches "per'hour.
  • Eicizr'ri' 'pl lV Anadherent continuous nickel-boron plate was formed at an average rate of 0.014X10 inches per hour on a carbonsteel -panel by immersing it in a plating solution at-24" C. for 127 minutes.
  • the plating solution contained 1.1 wt. percent (CH N-BH 5.1 wt. percent NiCl and '93.8% water.
  • Example V "Afca'rbon"s'fe e1'testpanel was immersed in a plating solution containing 2.2'wt.percent (CH NH-BH 5.1 f'wt.percent CcCl and 92.7 wt. percent water.
  • the avera'geplating rate was 0. O3 10* inches per hour for a two fh mmersion at'roomtemperature. During the plating reaction a small amount of particulate boron alloy precipitate was formed.
  • a 'carbon steel panel was immersed inthe solution at room ternperature for 297 minutes.
  • a bright plate of cobaltboron'alloy' was plated on'the panel at an average rate of 0.25X1Q' inches per hour.
  • the jniclgel-boron coatings formed by theprocess of j thisinvention' generally appear dark to semi-bright and the cobaltboron coatings generally appear semi-bright to bright.
  • the plated alloys contain from about 4 to 10 "pe ssa ihom .7 -Accordingto'theprovisions of the patent statutes, I have explained the principleand mode of practicing my 'iin entiOn'Qand haVe described what I'nowconsider to be its: best embodiments. However, I desire'to have it midersto'od' that within the scope of the appended claims,
  • An aqueous chemical plating solution containing as essential components (1) a compound selected from the group consisting of secondaryand tertiary amine boranes and, (2) acompound selected'from the groupconsisting 'of soluble saltsof nickel and cobalt, the proportions of 'each' component being such that'the concentration' of borane radical isbetween'about 0.1 to 3 wt. percent, and the concentration of metal ion is between about 0.02 and 6 wt. percent.
  • a method of plating metal-boron alloys on metal "objects which comprises the step ofconta cting the object to be plated with an aqueous plating solution containing as essential components (1) a compound selected from the group consisting of secondary and tertiary amine boranes and. (2) a compound selected from the group consisting of soluble salts of nickel and cobalt, the proportions of each component being such that the concentration of borane radical is between about 0.1 to 3 wt. percent and the concentration'of metal ion is between about 0.02 and 6 wt. percent.

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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)

Description

United States Patent Pennsylvania I No Drawing. Filed Aug. 5, 1958, Ser. No. 753,192
8 Claims. (Cl. 117-130) This invention relates to a method of chemical plating and more particularly to a method of plating metal objects with metal-boron alloys.
Nickel-boron and cobalt-boron alloys are known for their superior flowing properties, wear resistance, and hardness. Metal boron alloys, or metal borides, are particularly useful as coatings for steel and other metals that do not possess these desirable properties. The metalboron alloys are also useful as catalysts for a number of chemical reactions, e.g., hydrogenation reactions. Coatings of metal-boron alloys on other metallic base materials are particularly desirable as catalysts since a maximum amount of catalytic surface is provided by a minimum amount of the metal-boron alloy.
This invention is based on my discovery that an aqueous solution of an amine borane, X-BI-l Where X is an amine, and a soluble nickel or cobalt salt is a stable chemical plating solution. When a material with a catalytically active surface is contacted with this plating solution, a reaction occurs at the surface forming an adherent continuous plate of metal-boron alloy on the surface. The alloy plate itself is catalytically active so that the surface reaction can be continued to form a plate of any desired thickness. I have found that any clean metal surface, free of oxide film, is catalytically active. Glass, waxes, e.g. paraifinic waxes, natural fibers, and synthetic organic polymers, e.g. polyethylene and nylon, exhibit essentially no catalytic activity.
The solution or plating bath of this invention comprises an aqueous solution containing from about: (1) 0.02 to 6 parts by weight metal ion of the metal boron alloy to be plated, and (2) 0.1 to 3 parts by weight of boraneradical, EH
The metal ion, i.e. cobalt, or nickel ion, is provided by use of any soluble metal salt such as nickel sulfate, nickel chloride, nickel acetate, cobaltoussulfate, cobaltous chloride or other suitable soluble salts.
The borane radical is provided by the use of any secondary or tertiary amine borane, e.g. trimethylamine borane, dimethylamine borane, tripropylamine borane, pyridine borane and lutidine borane. Primary amine boranes are not satisfactory for use in the plating baths because they are rapidly decomposed by hydrolysis reactions.
The pH of the plating baths should be maintained below about 6.5; at higher pH values the plating reaction is extremely slow and some metal ion precipitates as the hydroxide. It is preferred to maintain the pH above about 2 because at lower pH values the solution is only metastable and tends to react spontaneously forming a large amount of particulate precipitate so that only a small proportion of the metal-boron alloy is plated. The initial pH of the aqueous plating solutions containing the metal salt and the amine borane are within the preferred range. As the plating reaction proceeds the pH of the solution increases because of the release of amine from the reacted amine borane. If the pH increases to too high a value, the solution can be acidified with any non-oxidizing acid, e.g. HCl. It is particularly convenient to buffer the plating solution with a weak, non-oxidizing acid, e.g. acetic acid or boric acid.
The plating baths of this invention have varying degrees of activity; the more active baths plate at a higher rate. The activity of the bath increases with increasing metal 2,990,296 Patented June 27, 1951 p ce 2 ion concentration and increasing borane radical concentration. The activity of the bath also increases with a decrease in pH. The plating bath may be used at any temperature between about room temperature and the boiling point of the solution with the activity of the bath increasing with increasing temperature.
The object to be plated is immersed in the plating bath and the plating commences. The object may conveniently be suspended by a string or rope made of-natural or synthetic fiber, or it may be suspended in a cloth or supported by a wood, glass, or synthetic polymer rack. If a metal piece is used to support the object to be plated, some of the bath will be consumed in plating the support. After the object has been plated, it is removed from the bath and washed with water to remove the bath solution and permitted to dry.
Metal objects to be plated must have clean surfaces free of oxide film. The objects are cleaned by any of the conventional cleaning procedures. The clean metal surface'catalyzes the chemical reduction reaction which results in a metal-boron alloy plate on the clean surface.
'Objects of steel, iron, nickel, cobalt, titanium, copper and copper base alloys, aluminum and aluminum base alloys, palladium, and other metals may be plated according to this invention.
It is preferred to contain the plating solution in a vessel that exposes only non-active surfaces to the bath. Glass vessels are most convenient, and synthetic polymer vessels, such as polyethylene vessels, and vessels lined with nonactive material may be ued, e.g., paraffin Wax lined, polyethylene lined, or polyvinylidine chloride lined vessels. The plating process is then selective; the plating occurs on the metal object immersed in the solution and does not occur on the vessel walls.
When plating has proceeded for several hours, a small amount of metal-boron alloy particulate precipitate is formed and collects at the bottom of the vessel. This precipitate is itself catalytically active so that if it is not removed some of the plating solution will be consumed by reaction induced by the precipitate. The precipitate may be removed by filtration.
The chemical plating consumes borane radical and metal ion; any desired concentration or concentration range may be maintained by adding additional amine borane or metal salts to the plating solution.
The following examples are illustrative of the plating solutions of this invention. The compositions of the solutions are expressed in weight percent of anhydrous reactants. The actual metal salts used were hydrates.
individual metal strips in aliquots of the plating solution for two hours at about 25 C Example II A plating solution was prepared which contained 0.95 wt. percent (CH NH-BH 5.14 wt. percent NiCl and 93.91 wt. percent water. The pH of the solution was 5.4. A carbon steel test panel was immersed in the solution maintained at 18 C. for 2 /3 hours. A nickel-boron alloy immediately started to plate on the steel panel. During the course of the plating reaction the pH increased to 6.13
and the rate of plating"decreased. The average rate of plate-deposition was-0.019 inches per'hour.
Exahiple [II 1:56 ate of fiofmatiori at mm allo plate is incr ased if t li solution ismiiifei'ed to reduce-the? increasedn pH (hiring thecouiseof' the reaction. For example. a buffered solution:contairiing' 3.7 'wt. percent (CH NH-BH ,9.3 wt. percenmsic1 wt; percent'H BO and 284.5 wt. percent water had-'apHof tQS. A nickel-boronalloy "was pl'ated'z on a" carbonsteel panel immersed in the solutionfo r 6%h ours at" 18 C. The average plating rate was 0.091 X1 0- inches "per'hour.
Eicizr'ri' 'pl lV Anadherent continuous nickel-boron plate was formed at an average rate of 0.014X10 inches per hour on a carbonsteel -panel by immersing it in a plating solution at-24" C. for 127 minutes. The plating solution contained 1.1 wt. percent (CH N-BH 5.1 wt. percent NiCl and '93.8% water. a
. Example V "Afca'rbon"s'fe e1'testpanelwas immersed in a plating solution containing 2.2'wt.percent (CH NH-BH 5.1 f'wt.percent CcCl and 92.7 wt. percent water. The avera'geplating rate was 0. O3 10* inches per hour for a two fh mmersion at'roomtemperature. During the plating reaction a small amount of particulate boron alloy precipitate was formed.
. Example VI bufiered' platingsolution containing 3.7 wt. percent 1((3 I-I3') NH-BH 10.1 wt. percent CoCl 2.5 wt. percent I- IBQ and 83.7wt. percent water hada pH of 4.02. A 'carbon steel panelwas immersed inthe solution at room ternperature for 297 minutes. A bright plate of cobaltboron'alloy'was plated on'the panel at an average rate of 0.25X1Q' inches per hour. The jniclgel-boron coatings formed by theprocess of j thisinvention'generally appear dark to semi-bright and the cobaltboron coatings generally appear semi-bright to bright. f The plated alloys contain from about 4 to 10 "pe ssa ihom .7 -Accordingto'theprovisions of the patent statutes, I have explained the principleand mode of practicing my 'iin entiOn'Qand haVe described what I'nowconsider to be its: best embodiments. However, I desire'to have it midersto'od' that within the scope of the appended claims,
the invention may be practiced otherwise than as specifically described.
I claim:
1. An aqueous chemical plating solution containing as essential components (1) a compound selected from the group consisting of secondaryand tertiary amine boranes and, (2) acompound selected'from the groupconsisting 'of soluble saltsof nickel and cobalt, the proportions of 'each' component being such that'the concentration' of borane radical isbetween'about 0.1 to 3 wt. percent, and the concentration of metal ion is between about 0.02 and 6 wt. percent.
2. A method of plating metal-boron alloys on metal "objects which comprises the step ofconta cting the object to be plated with an aqueous plating solution containing as essential components (1) a compound selected from the group consisting of secondary and tertiary amine boranes and. (2) a compound selected from the group consisting of soluble salts of nickel and cobalt, the proportions of each component being such that the concentration of borane radical is between about 0.1 to 3 wt. percent and the concentration'of metal ion is between about 0.02 and 6 wt. percent.
3. A method according to claim 2 in which the amine borane is dimethylamine borane.
4. A method according to claim 2 in which the pH of the plating solutionis maintained between about 2 and 6.5.
References Cited in the file of this patent V UNITED STATES PATENTS Schlesinger et al. Feb. 15, 1949 Warf Dec. 6, 1955 OTHER REFERENCES 'Hurdi Chemistry of the Hydrides, 1952 John Wiley 'andSons, pg. 84.
Notice of Adverse Decision in Interference In Interference No. 93,4:69 involving Patent No. 2,990,296, R. M. Hoke, Chemical plating of metal-boron alloys, final judgment adverse to the patentee was rendered Nov. 24:, 1964:, as to claims 1, 2, 3, 4c, 5, 7 and 8.
[Ofiioial Gazette J ammry 1.9, 1965.]

Claims (1)

  1. 2. A METHOD OF PLASING METAL-BORON ALLY ON METAL OBJECTS WHICH COMPRISES THE STEP OF CONTACTING THE OBJECT TO BE PLATED WITH AN AQUEOUS PLATING SOLUTION CONTAINING AS ESSENTIAL COMPONENTS (1) A COMPOUND SELECTED FROM THE GROUP CONSISTING OF SECONDARY AND TERTIARY AMINE BORANES AND, (2) A COMPOUND SELECTED FROM THE GROUP CONSISTING OF SOLUBLE SALTS OF NICKEL AND COBALT, THE PROPORTIONS OF EACH COMPONENT BEING SUCH THAT THE CONCENTRATION OF BORANE RADICAL IS BETWEEN ABOUT 0.1 TO 3 WT. PERCENT AND THE CONCENTRATION OF METAL ION IS BETWEEN ABOUT 0.02 AND 6 WT. PERCENT.
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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3063850A (en) * 1959-09-11 1962-11-13 Metal Hydrides Inc Metal plating by chemical reduction with amine boranes
US3140188A (en) * 1960-08-29 1964-07-07 Bayer Ag Bath compositions for chemical plating of metals containing boron nitrogen compounds nd an organic solubilizing compound
US3246994A (en) * 1962-01-17 1966-04-19 Transitron Electronic Corp Plating semiconductor materials
US3247028A (en) * 1961-06-28 1966-04-19 Bayer Ag Processes for improving the corrosion resistance of ni-co-metal coatings containing boron
US3268422A (en) * 1960-06-09 1966-08-23 Nat Steel Corp Electroplating bath containing aluminum and manganese-bearing materials and method of forming aluminummanganese alloy coatings on metallic bases
US3295999A (en) * 1960-12-31 1967-01-03 Bayer Ag Process of chemical metal plating and baths therefor
US3338726A (en) * 1958-10-01 1967-08-29 Du Pont Chemical reduction plating process and bath
US3431120A (en) * 1966-06-07 1969-03-04 Allied Res Prod Inc Metal plating by chemical reduction with amineboranes
US3656952A (en) * 1968-07-19 1972-04-18 Minnesota Mining & Mfg Non-reversal imaging process and recording elements produced thereby
US3925578A (en) * 1971-07-29 1975-12-09 Kollmorgen Photocircuits Sensitized substrates for chemical metallization
US4361602A (en) * 1980-09-13 1982-11-30 Agency Of Industrial Science & Technology Method for production of positive electrode for electrolysis of water
US4484988A (en) * 1981-12-09 1984-11-27 Richmond Metal Finishers, Inc. Process for providing metallic articles and the like with wear-resistant coatings
US4515869A (en) * 1981-07-22 1985-05-07 Allied Corporation Homogeneous, ductile nickel based hardfacing foils
US4833041A (en) * 1986-12-08 1989-05-23 Mccomas C Edward Corrosion/wear-resistant metal alloy coating compositions
US5019163A (en) * 1986-12-08 1991-05-28 Mccomas C Edward Corrosion/wear-resistant metal alloy coating compositions
WO1992005952A1 (en) * 1990-10-09 1992-04-16 Diamond Technologies Company Nickel-cobalt-boron alloy, implement, plating solution and method for making
US6183546B1 (en) 1998-11-02 2001-02-06 Mccomas Industries International Coating compositions containing nickel and boron

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2461661A (en) * 1945-01-09 1949-02-15 Hermann I Schlesinger Preparation of alkali metal compounds
US2726170A (en) * 1954-09-07 1955-12-06 Superweld Corp Method of coating steel with nickel-boron

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2461661A (en) * 1945-01-09 1949-02-15 Hermann I Schlesinger Preparation of alkali metal compounds
US2726170A (en) * 1954-09-07 1955-12-06 Superweld Corp Method of coating steel with nickel-boron

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3338726A (en) * 1958-10-01 1967-08-29 Du Pont Chemical reduction plating process and bath
US3063850A (en) * 1959-09-11 1962-11-13 Metal Hydrides Inc Metal plating by chemical reduction with amine boranes
US3268422A (en) * 1960-06-09 1966-08-23 Nat Steel Corp Electroplating bath containing aluminum and manganese-bearing materials and method of forming aluminummanganese alloy coatings on metallic bases
US3140188A (en) * 1960-08-29 1964-07-07 Bayer Ag Bath compositions for chemical plating of metals containing boron nitrogen compounds nd an organic solubilizing compound
US3295999A (en) * 1960-12-31 1967-01-03 Bayer Ag Process of chemical metal plating and baths therefor
US3247028A (en) * 1961-06-28 1966-04-19 Bayer Ag Processes for improving the corrosion resistance of ni-co-metal coatings containing boron
US3246994A (en) * 1962-01-17 1966-04-19 Transitron Electronic Corp Plating semiconductor materials
US3431120A (en) * 1966-06-07 1969-03-04 Allied Res Prod Inc Metal plating by chemical reduction with amineboranes
US3656952A (en) * 1968-07-19 1972-04-18 Minnesota Mining & Mfg Non-reversal imaging process and recording elements produced thereby
US3925578A (en) * 1971-07-29 1975-12-09 Kollmorgen Photocircuits Sensitized substrates for chemical metallization
US4361602A (en) * 1980-09-13 1982-11-30 Agency Of Industrial Science & Technology Method for production of positive electrode for electrolysis of water
US4515869A (en) * 1981-07-22 1985-05-07 Allied Corporation Homogeneous, ductile nickel based hardfacing foils
US4484988A (en) * 1981-12-09 1984-11-27 Richmond Metal Finishers, Inc. Process for providing metallic articles and the like with wear-resistant coatings
US4833041A (en) * 1986-12-08 1989-05-23 Mccomas C Edward Corrosion/wear-resistant metal alloy coating compositions
US5019163A (en) * 1986-12-08 1991-05-28 Mccomas C Edward Corrosion/wear-resistant metal alloy coating compositions
WO1992005952A1 (en) * 1990-10-09 1992-04-16 Diamond Technologies Company Nickel-cobalt-boron alloy, implement, plating solution and method for making
US5314608A (en) * 1990-10-09 1994-05-24 Diamond Technologies Company Nickel-cobalt-boron alloy, implement, plating solution and method for making same
US6183546B1 (en) 1998-11-02 2001-02-06 Mccomas Industries International Coating compositions containing nickel and boron

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