US3432338A - Electroless nickel,cobalt and nickel-cobalt alloy plating from fluoborates sources - Google Patents
Electroless nickel,cobalt and nickel-cobalt alloy plating from fluoborates sources Download PDFInfo
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- US3432338A US3432338A US632513A US3432338DA US3432338A US 3432338 A US3432338 A US 3432338A US 632513 A US632513 A US 632513A US 3432338D A US3432338D A US 3432338DA US 3432338 A US3432338 A US 3432338A
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- United States
- Prior art keywords
- cobalt
- nickel
- gallon
- fluoborate
- sodium
- Prior art date
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Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title description 72
- 229910052759 nickel Inorganic materials 0.000 title description 36
- 229910017052 cobalt Inorganic materials 0.000 title description 31
- 239000010941 cobalt Substances 0.000 title description 31
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title description 30
- 238000007747 plating Methods 0.000 title description 20
- 229910000531 Co alloy Inorganic materials 0.000 title description 15
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 16
- 239000001632 sodium acetate Substances 0.000 description 16
- 235000017281 sodium acetate Nutrition 0.000 description 16
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 16
- 239000001509 sodium citrate Substances 0.000 description 16
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 14
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 9
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 8
- 238000007792 addition Methods 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 8
- 229940044175 cobalt sulfate Drugs 0.000 description 8
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 7
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 238000007772 electroless plating Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 235000019589 hardness Nutrition 0.000 description 3
- -1 i.e. Substances 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 150000001455 metallic ions Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical class CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical class [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- SKYGTJFKXUWZMD-UHFFFAOYSA-N ac1l2n4h Chemical compound [Co].[Co] SKYGTJFKXUWZMD-UHFFFAOYSA-N 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical class [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
- C23C18/48—Coating with alloys
- C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
-
- 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
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
Definitions
- Another object of this invention is to provide additional stress relief, ductility and activation within the structure of the nickel, cobalt or nickel-cobalt-alloy deposits by electroless plating in a solution whose total metallic source consists of nickel fluoborate, cobalt fluoborate, or a combination thereof.
- a further object of this invention is to provide versatile and very adaptable electroless nickel, cobalt and alloy plating baths by including the fluoborate ion in electroless plating solutions which are made up from conventional salts of nickel and cobalt such as nickel sulfate, cobalt sulfate, nickel chloride, cobalt chloride, etc., such fluobo rate ion being included by its addition to the baths in the form of fluoboric acid or any of the derivatives of fluoboric acid, i.e., nickel fluoborate, calcium fluoborate, sodium fluoborate, potassium fluoborate, etc.
- Yet another object of this invention is to deposit metallic coatings of such potential adhesion and zero-to-compressive internal stress that they may be applied directly to aluminum and magnesium surfaces without extensive pre-treatment and without the necessity of depositing other coatings between the aluminum or magnesium substrate and the nickel, cobalt or alloy coating being deposited from the solutions of the invention.
- Another object of this invention is to provide metallic coatings possessing such properties of adherence and voidfreeness that they may be applied to the surfaces of sensitized non-metallic materials such as ceramics, glass, rubber, epoxies, phenolics, acrylics, vinyls, polypropylenes, polyesters and other normally inert materials without the acquisition through such coating buildup of cracks and voids due to tensile stresses inherited from the stressed substrate.
- sensitized non-metallic materials such as ceramics, glass, rubber, epoxies, phenolics, acrylics, vinyls, polypropylenes, polyesters and other normally inert materials
- Yet another object of this invention is to provide a number, of autocatalytic or electroless plating solutions which will deposit nickel, cobalt or nickel-cobalt-alloy coatings upon the surfaces of metallic and non-metallic materials at a buildup rate within the range of .0001 and .0015 inch per hour of plating time, such deposition rate being dependent upon, and controlled by, temperature, agitation rate, pH and chemical concentrations, such deposited coating having a Rockwell C hardness in the range of 32 to 45 as plated, and capable of a hardness increase in the range of 25% to 35% over the asplated condition by being heated to a temperature range within 500 and 800 F., allowing to dwell at this temperature for 3 to 6 hours and cooled in air to ambient temperature.
- Hardnesses within the above ranges may also be obtained by accelerated aging, i.e., heating the as-plated coatings to a temperature within the range of 180 to 280 F., maintaining this temperature for a period of 8 to 16 hours, and cooling in air to ambient temperature.
- a further object of this invention is to provide fluoboric acid or fluoborate addition agents for use in electroless nickel, cobalt or alloy plating solutions, such addition agents being buffered, if necessary, to a pH in a range suitable for use in raising or lowering the acidity or alkalinity of the plating solution and having the functions of enhancing ductility, grain refinement and appearance of the metallic coatings as well as accelerating the rate of deposit and providing pH control of the plating solution.
- this invention relates to a number of novel and unique solutions for use in the electroless deposition of nickel, cobalt or nickel cobalt alloys and these baths comprise between about 0.1 and 35.0 oz./gal. of nickel and/or cobalt fluoborate, 0.05 to 35.0 oz./ gal. of addition agents from the group consisting of fluoboric acid or its fluoborate derivatives, i.e., ammonium fluoborate, sodium fluoborate, potassium fluoborate, etc., 0.1 to 5 oz./gal. sodium citrate, 0.1 to 5 oz./gallon sodium acetate and 0.2 to 8 oz./gallon sodium hypophosphite.
- fluoboric acid or its fluoborate derivatives i.e., ammonium fluoborate, sodium fluoborate, potassium fluoborate, etc.
- fluoboric acid or its fluoborate derivatives i.e., ammonium fluoborate,
- the present invention also relates to the method of depositing metallic coatings through use of the above materials from solutions in which the temperature is maintained within the range of 40 F. and 210 F., the pH between 0.5 and 14.5 and the metallic content within the range of 0.05 and 15.0 oz./ gallon.
- the fluoborate bath (cobalt) Cobalt fluoborate 0.1-35.0 Sodium citrate 0.1-5.0 Sodium acetate 0.1 5.0 Sodium hypophosphite 0.28.0
- the fluoborate bath nickel-cobalt alloy
- Nickel fluoborate-l-cobalt fluoborate 1 0.1-35.0 Sodium citrate 0.1-5.0 Sodium acetate 0.1-5 .0 Sodium hypophosphite 0.2-8.0
- Ni'rn.-The nickel chloride salt may be mixed with or substituted for the sulfate.
- the sulfate-fluobonate bath (cobalt) Cobalt fluoborate-l-cobalt sulfate 1 0.1-35.0 Sodium citrate 0.1-5.0 Sodium acetate 0.1-5.0 Sodium hypophosphite 0.2-8.0
- the sulfate-fluoborate bath nickel-cobalt alloy
- Nickel fluoborate-i-cobalt sulfate 1 0.1-35.0
- cobalt chloride salt may be mixed with or substituted for the sulfate.
- Nickel bath (ammonium fluoborate added) Nickel sulfate 0.1-35 .0 Sodium citrate 0.1-5.0 Sodium acetate 0.1-5 .0 Ammonium fluoborate 0.1-35.0
- No'ru.'lhe nickel salt may be mixed with or substituted for the sulfate.
- the cobalt bath (ammonium fluoborate added) Cobalt sulfate 0.1-35.0 Sodium citrate 0.1-5.0 Sodium acetate 0.1-5.0 Ammonium fluoborate 0.1-35 .0
- the cobalt chloride salt may be mixed with or substituted for the sulfate.
- ammonium, calcium or potassium salts of citrate, acetate or hypophosphite may be substituted for the sodium salt in all of the claimed solutions of the invention without departing from the purpose or scope thereof.
- a solution for use in electroless nickel, cobalt or nickel-cobalt-alloy plating comprising between 0.1 and 35.0 oz./ gallon of one or more materials from the group consisting of nickel sulfate, cobalt sulfate, nickel chloride and cobalt chloride between 0.1 and 5.0 oz./ gallon sodium citrate, 0.1 and 5.0 oz./gallon sodium acetate, between 0.2 to 8.0 oz./gallon sodium hypophosphite and between 0.005 and 50.0 oz./gallon fluoboric acid.
- a method of nickel, cobalt or nickel-cobalt-alloy electroless plating comprising the steps of forming a bath from about 0.1 to 35.0 oz./ gallon nickel fluoborate, cobalt fluoborate or a combination thereof, between 0.1 and 5.0 oz./ga1l0n sodium citrate, between 0.1 and 5.0 oz./gallon sodium acetate, between 0.2 to 8.0 oz./gallon sodium hypophosphite, immersing a metallic or nonmetallic article into the bath and causing nickel, cobalt or alloy plating to be deposited on the article while maintaining the solution at a temperature within the range of 40 F. and 210 F. and at a pH within the range of 0.5 to 14.5, and maintaining the strength of the solution by regular additions of its constituents.
- a method of nickel, cobalt or nickel-cobalt-alloy plating comprising the steps of forming a bath from about 0.1 to 35.0 oz./gallon of one or more materials from the group consisting of nickel and cobalt sources of metallic ions, between 0.1 and 5.0 oz./gallon sodium citrate, between 0.1 and 5.0 oz./gallon sodium acetate, between 0.2 and 8.0 oz./ gallon sodium hypophosphite and between 0.005 and 50.0 oz./ gallon of one or more materials from the group consisting of fluoboric acid, ammonium fluoborate, calcium fluoborate, potassium fiuoborate and sodium fluoborate, immersing a metallic or nonmetallic article into the bath and causing nickel, cobalt or alloy plating to be deposited on the article while maintaining the solution at a temperature within the range of 40 F. and 210 F. and at a pH within the range of 0.5 to 14.5, and maintaining the strength
- a method of nickel, cobalt or nickel-cobalt-alloy plating comprising the steps of forming a bath from 0.1 to 35.0 oz./gallon of one or more materials from the group consisting of nickel and cobalt sources of metallic ions, between 0.1 and 5.0 oz./gallon sodium citrate, between 0.1 and 5.0 oz./ gallon sodium acetate, between 0.2 and 8.0 oz./gallon sodium hypophosphite and between 5 6 0.005 and 50.0 oz./-gallon of one or more materials from References Cited the group consisting of fluoboric acid, ammonium fluo- UNITED STATES PATENTS borate, calcium fluoborate, potassium fluoborate and sodium fluoborate which have been buffered by alkaline or gfig igg'g 'g ist 7:3 acid reagents to a pH within the range necessary to control 5 3378400 4/1968 Sickles the pH of the solution
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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 9 Claims ABSTRACT OF THE DISCLOSURE The invention hereinafter described relates to novel methods of autocatalytic or commonly called electroless plating of nickel, cobalt and their common alloys, and further employs fluoborate solutions and methods for their use in producing nickel, cobalt and alloy deposits by non-electrolytic means, such deposits having the quali ties of superior corrosion resistance, zero-to-compressive internal stresses and excellent hardenability characteristics under ordinary heat-treating or accelerated aging processes.
This is a continuation-in-part of my patent specification Serial No. 476,183, filed July 30, 1965, now Patent Number 3,378,400 issued Apr. 16, 1968.
Another object of this invention is to provide additional stress relief, ductility and activation within the structure of the nickel, cobalt or nickel-cobalt-alloy deposits by electroless plating in a solution whose total metallic source consists of nickel fluoborate, cobalt fluoborate, or a combination thereof.
A further object of this invention is to provide versatile and very adaptable electroless nickel, cobalt and alloy plating baths by including the fluoborate ion in electroless plating solutions which are made up from conventional salts of nickel and cobalt such as nickel sulfate, cobalt sulfate, nickel chloride, cobalt chloride, etc., such fluobo rate ion being included by its addition to the baths in the form of fluoboric acid or any of the derivatives of fluoboric acid, i.e., nickel fluoborate, calcium fluoborate, sodium fluoborate, potassium fluoborate, etc.
It is a further object of this invention to provide metallic coatings which are relatively soft and very receptive to subsequent plating deposits of chromium, brass, palladium, rhodium, nickel, etc., by chemically plating a deposit from nickel fluoborate, cobalt fluoborate or a combination thereof, without the addition of fluoboratetype, non-metallic derivatives.
Yet another object of this invention is to deposit metallic coatings of such potential adhesion and zero-to-compressive internal stress that they may be applied directly to aluminum and magnesium surfaces without extensive pre-treatment and without the necessity of depositing other coatings between the aluminum or magnesium substrate and the nickel, cobalt or alloy coating being deposited from the solutions of the invention.
Another object of this invention is to provide metallic coatings possessing such properties of adherence and voidfreeness that they may be applied to the surfaces of sensitized non-metallic materials such as ceramics, glass, rubber, epoxies, phenolics, acrylics, vinyls, polypropylenes, polyesters and other normally inert materials without the acquisition through such coating buildup of cracks and voids due to tensile stresses inherited from the stressed substrate.
Yet another object of this invention is to provide a number, of autocatalytic or electroless plating solutions which will deposit nickel, cobalt or nickel-cobalt-alloy coatings upon the surfaces of metallic and non-metallic materials at a buildup rate within the range of .0001 and .0015 inch per hour of plating time, such deposition rate being dependent upon, and controlled by, temperature, agitation rate, pH and chemical concentrations, such deposited coating having a Rockwell C hardness in the range of 32 to 45 as plated, and capable of a hardness increase in the range of 25% to 35% over the asplated condition by being heated to a temperature range within 500 and 800 F., allowing to dwell at this temperature for 3 to 6 hours and cooled in air to ambient temperature. Hardnesses within the above ranges may also be obtained by accelerated aging, i.e., heating the as-plated coatings to a temperature within the range of 180 to 280 F., maintaining this temperature for a period of 8 to 16 hours, and cooling in air to ambient temperature.
A further object of this invention is to provide fluoboric acid or fluoborate addition agents for use in electroless nickel, cobalt or alloy plating solutions, such addition agents being buffered, if necessary, to a pH in a range suitable for use in raising or lowering the acidity or alkalinity of the plating solution and having the functions of enhancing ductility, grain refinement and appearance of the metallic coatings as well as accelerating the rate of deposit and providing pH control of the plating solution.
In general, this invention relates to a number of novel and unique solutions for use in the electroless deposition of nickel, cobalt or nickel cobalt alloys and these baths comprise between about 0.1 and 35.0 oz./gal. of nickel and/or cobalt fluoborate, 0.05 to 35.0 oz./ gal. of addition agents from the group consisting of fluoboric acid or its fluoborate derivatives, i.e., ammonium fluoborate, sodium fluoborate, potassium fluoborate, etc., 0.1 to 5 oz./gal. sodium citrate, 0.1 to 5 oz./gallon sodium acetate and 0.2 to 8 oz./gallon sodium hypophosphite. The present invention also relates to the method of depositing metallic coatings through use of the above materials from solutions in which the temperature is maintained within the range of 40 F. and 210 F., the pH between 0.5 and 14.5 and the metallic content within the range of 0.05 and 15.0 oz./ gallon.
Although the number of various and different operable plating solutions made possible by the use of fluoboric acid and its many fluoborate derivatives are virtually impossible to list within the pages of this specification, a few of the more common and typical solutions are as follows:
The fluoborate bath (nickel) Oz./ gallon Nickel fluoborate 0.1-35.0 Sodium citrate 0.1-5.0 Sodium acetate 0.1-5.0 Sodium hypophosphite 0.2-8.0
The fluoborate bath (cobalt) Cobalt fluoborate 0.1-35.0 Sodium citrate 0.1-5.0 Sodium acetate 0.1 5.0 Sodium hypophosphite 0.28.0
The fluoborate bath (nickel-cobalt alloy) Nickel fluoborate-l-cobalt fluoborate 1 0.1-35.0 Sodium citrate 0.1-5.0 Sodium acetate 0.1-5 .0 Sodium hypophosphite 0.2-8.0
1 Any ratio.
1 Any ratio. N'rn.-The nickel chloride salt may be mixed with or substituted for the sulfate.
The sulfate-fluobonate bath (cobalt) Cobalt fluoborate-l-cobalt sulfate 1 0.1-35.0 Sodium citrate 0.1-5.0 Sodium acetate 0.1-5.0 Sodium hypophosphite 0.2-8.0
1 Any ratio. NOTE.--Tlle cobalt chloride salt may be mixed with or substituted for the sulfate.
The sulfate-fluoborate bath (nickel-cobalt alloy) Nickel fluoborate-i-cobalt sulfate 1 0.1-35.0
Sodium citrate 0.1-5.0
Sodium acetate 0.1-5.0
Sodium hypophosphite 0.2-8.0
1 Any ratio.
Nora-The cobalt chloride salt may be mixed with or substituted for the sulfate.
The nickel bath (ammonium fluoborate added) Nickel sulfate 0.1-35 .0 Sodium citrate 0.1-5.0 Sodium acetate 0.1-5 .0 Ammonium fluoborate 0.1-35.0
No'ru.'lhe nickel salt may be mixed with or substituted for the sulfate.
The cobalt bath (ammonium fluoborate added) Cobalt sulfate 0.1-35.0 Sodium citrate 0.1-5.0 Sodium acetate 0.1-5.0 Ammonium fluoborate 0.1-35 .0
No'rn.The cobalt chloride salt may be mixed with or substituted for the sulfate.
Sodium, potassium, calcium, or other fluoborate, or fluoboric acid may be used in the foregoing baths of the invention without departing from the scope and spirit of this specification.
The ammonium, calcium or potassium salts of citrate, acetate or hypophosphite may be substituted for the sodium salt in all of the claimed solutions of the invention without departing from the purpose or scope thereof.
While a complete embodiment of the invention has been disclosed, it will be appreciated that modification of this particular embodiment of the invention may be resorted to without departing from the scope of the invention as defined in the appended claims.
What is claimed is:
1. A solution for use in electroless nickel, cobalt or nickel-cobalt-alloy plating and comprising between 0.1 to 35.0 oz./gallon of one or more materials from the group consisting of nickel and cobalt fluoborate sources, between 0.1 and 5.0 oz./gallon sodium citrate, 0.1 to 5.0 oz./gallon sodium acetate and 0.2 to 8.0 oz./gallon sodium hypophosphite.
2. A solution for use in electroless nickel, cobalt or nickel-cobalt-alloy plating and comprising between 0.1 and 35.0 oz./gallon of one or more materials from the group consisting of nickel sulfate, cobalt sulfate, nickel chloride and nickel chloride between 0.1 and 5.0 oz./ gallon sodium citrate, 0.1 and 5.0 oz./gallon sodium acetate, between 0.2 to 8.0 oz./ gallon sodium hypophosphite and between 0.005 and 50.0 oz./gallon sodium fluoroborate.
3. A solution for use in electroless nickel, cobalt or nickel-cobalt-alloy plating and comprising between 0.1 and 35.0 oz./gallon of one or more materials from the group consisting of nickel sulfate, cobalt sulfate, nickel chloride and nickel chloride between 0.1 and 5.0 oz./ gallon sodium citrate, 0.1 and 5.0 oz./gallon sodium acetate, between 0.2 to 8.0 oz./gallon sodium hypophosphite and between 0.005 and 50.0 oz./gallon calcium fiuoborate.
4. A solution for use in electroless nickel, cobalt or nickel-cobalt-alloy plating and comprising between 0.1 and 35.0 oz./ gallon of one or more materials from the group consisting of nickel sulfate, cobalt sulfate, nickel chloride and cobalt chloride between 0.1 and 5.0 oz./ gallon sodium citrate, 0.1 and 5.0 oz./gallon sodium acetate, between 0.2 to 8.0 02/ gallon sodium hypophosphite and between 0.005 and 50.0 oz./gallon potassium fluoborate.
5. A solution for use in electroless nickel, cobalt or nickel-cobalt-alloy plating and comprising between 0.1 and 35:0 oz./gallon of one or more materials from the group consisting of nickel sulfate, cobalt sulfate, nickel chloride and cobalt chloride between 0.1 and 5.0 oz./ gallon sodium citrate, 0.1 and 5.0 oz./gallon sodium acetate, between 0.2 to 8.0 oz./ gallon sodium hypophosphite and between 0.005 and 50.0 oz./gallon ammonium fiuoborate.
6. A solution for use in electroless nickel, cobalt or nickel-cobalt-alloy plating and comprising between 0.1 and 35.0 oz./ gallon of one or more materials from the group consisting of nickel sulfate, cobalt sulfate, nickel chloride and cobalt chloride between 0.1 and 5.0 oz./ gallon sodium citrate, 0.1 and 5.0 oz./gallon sodium acetate, between 0.2 to 8.0 oz./gallon sodium hypophosphite and between 0.005 and 50.0 oz./gallon fluoboric acid.
7. A method of nickel, cobalt or nickel-cobalt-alloy electroless plating comprising the steps of forming a bath from about 0.1 to 35.0 oz./ gallon nickel fluoborate, cobalt fluoborate or a combination thereof, between 0.1 and 5.0 oz./ga1l0n sodium citrate, between 0.1 and 5.0 oz./gallon sodium acetate, between 0.2 to 8.0 oz./gallon sodium hypophosphite, immersing a metallic or nonmetallic article into the bath and causing nickel, cobalt or alloy plating to be deposited on the article while maintaining the solution at a temperature within the range of 40 F. and 210 F. and at a pH within the range of 0.5 to 14.5, and maintaining the strength of the solution by regular additions of its constituents.
8. A method of nickel, cobalt or nickel-cobalt-alloy plating comprising the steps of forming a bath from about 0.1 to 35.0 oz./gallon of one or more materials from the group consisting of nickel and cobalt sources of metallic ions, between 0.1 and 5.0 oz./gallon sodium citrate, between 0.1 and 5.0 oz./gallon sodium acetate, between 0.2 and 8.0 oz./ gallon sodium hypophosphite and between 0.005 and 50.0 oz./ gallon of one or more materials from the group consisting of fluoboric acid, ammonium fluoborate, calcium fluoborate, potassium fiuoborate and sodium fluoborate, immersing a metallic or nonmetallic article into the bath and causing nickel, cobalt or alloy plating to be deposited on the article while maintaining the solution at a temperature within the range of 40 F. and 210 F. and at a pH within the range of 0.5 to 14.5, and maintaining the strength of the bath by regular additions of its constituents.
9. A method of nickel, cobalt or nickel-cobalt-alloy plating comprising the steps of forming a bath from 0.1 to 35.0 oz./gallon of one or more materials from the group consisting of nickel and cobalt sources of metallic ions, between 0.1 and 5.0 oz./gallon sodium citrate, between 0.1 and 5.0 oz./ gallon sodium acetate, between 0.2 and 8.0 oz./gallon sodium hypophosphite and between 5 6 0.005 and 50.0 oz./-gallon of one or more materials from References Cited the group consisting of fluoboric acid, ammonium fluo- UNITED STATES PATENTS borate, calcium fluoborate, potassium fluoborate and sodium fluoborate which have been buffered by alkaline or gfig igg'g 'g ist 7:3 acid reagents to a pH within the range necessary to control 5 3378400 4/1968 Sickles the pH of the solution within desired limits, immersing u a metallic or non-metallic article into the bath and caus- OTHER REFERENCES ing nickel, cobalt or alloy plating to be deposited on the Serota, Metal Finishing, August 1962, pp. 64, 65.
article while maintaining the solution at a temperature RALPH S KENDALL P E within the range of 40 F. and 210 F. and at a pH within 10 mmme" the range of 0.5 to 14.5, and maintaining the strength of US. Cl. X.R. the bath by regular additions of its constituents. 1061; 117-47, 160
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US63251367A | 1967-04-17 | 1967-04-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3432338A true US3432338A (en) | 1969-03-11 |
Family
ID=24535807
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US632513A Expired - Lifetime US3432338A (en) | 1967-04-17 | 1967-04-17 | Electroless nickel,cobalt and nickel-cobalt alloy plating from fluoborates sources |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3432338A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3622370A (en) * | 1969-04-07 | 1971-11-23 | Macdermid Inc | Method of and solution for accelerating activation of plastic substrates in electroless metal plating system |
| US3930896A (en) * | 1973-05-18 | 1976-01-06 | Tatsuta Densen Kabushiki Kaisha | Method for producing metal film resistor by electroless plating |
| US4055706A (en) * | 1974-07-16 | 1977-10-25 | Office National D'etudes Et De Recherches Aerospatiales (O.N.E.R.A.) | Processes for protecting refractory metallic components against corrosion |
| 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 |
| US5314608A (en) * | 1990-10-09 | 1994-05-24 | Diamond Technologies Company | Nickel-cobalt-boron alloy, implement, plating solution and method for making same |
| US5431804A (en) * | 1990-10-09 | 1995-07-11 | Diamond Technologies Company | Nickel-cobalt-boron alloy deposited on a substrate |
| US5494710A (en) * | 1994-07-05 | 1996-02-27 | Mallory, Jr.; Glenn O. | Electroless nickel baths for enhancing hardness |
| US5614003A (en) * | 1996-02-26 | 1997-03-25 | Mallory, Jr.; Glenn O. | Method for producing electroless polyalloys |
| US5804165A (en) * | 1996-07-24 | 1998-09-08 | Arnold; Michael J. | Antiplaque oral composition |
| US5965110A (en) * | 1990-11-02 | 1999-10-12 | Arnold; Michael J. | Plaque adsorbent oral composition and method |
| US6146702A (en) * | 1995-06-06 | 2000-11-14 | Enthone-Omi, Inc. | Electroless nickel cobalt phosphorous composition and plating process |
| US6183546B1 (en) | 1998-11-02 | 2001-02-06 | Mccomas Industries International | Coating compositions containing nickel and boron |
| US20070243044A1 (en) * | 2006-03-29 | 2007-10-18 | Chin-Chiu Chen | Wear resistant nut |
| EP2339050A1 (en) | 2001-10-24 | 2011-06-29 | Rohm and Haas Electronic Materials LLC | Stabilizers for electroless plating solutions and methods of use thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2313756A (en) * | 1939-03-01 | 1943-03-16 | Dow Chemical Co | Method of electroplating magnesium |
| US3155536A (en) * | 1962-06-06 | 1964-11-03 | Avco Corp | Aluminum oxidation resistant coating for nickel and cobalt base alloy parts |
| US3378400A (en) * | 1965-07-30 | 1968-04-16 | Ralph E. Sickles | Autocatalytic deposition of nickel, cobalt and alloys thereof |
-
1967
- 1967-04-17 US US632513A patent/US3432338A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2313756A (en) * | 1939-03-01 | 1943-03-16 | Dow Chemical Co | Method of electroplating magnesium |
| US3155536A (en) * | 1962-06-06 | 1964-11-03 | Avco Corp | Aluminum oxidation resistant coating for nickel and cobalt base alloy parts |
| US3378400A (en) * | 1965-07-30 | 1968-04-16 | Ralph E. Sickles | Autocatalytic deposition of nickel, cobalt and alloys thereof |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3622370A (en) * | 1969-04-07 | 1971-11-23 | Macdermid Inc | Method of and solution for accelerating activation of plastic substrates in electroless metal plating system |
| US3930896A (en) * | 1973-05-18 | 1976-01-06 | Tatsuta Densen Kabushiki Kaisha | Method for producing metal film resistor by electroless plating |
| US4055706A (en) * | 1974-07-16 | 1977-10-25 | Office National D'etudes Et De Recherches Aerospatiales (O.N.E.R.A.) | Processes for protecting refractory metallic components against corrosion |
| 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 |
| US5431804A (en) * | 1990-10-09 | 1995-07-11 | Diamond Technologies Company | Nickel-cobalt-boron alloy deposited on a substrate |
| US5314608A (en) * | 1990-10-09 | 1994-05-24 | Diamond Technologies Company | Nickel-cobalt-boron alloy, implement, plating solution and method for making same |
| US5965110A (en) * | 1990-11-02 | 1999-10-12 | Arnold; Michael J. | Plaque adsorbent oral composition and method |
| US5494710A (en) * | 1994-07-05 | 1996-02-27 | Mallory, Jr.; Glenn O. | Electroless nickel baths for enhancing hardness |
| US6146702A (en) * | 1995-06-06 | 2000-11-14 | Enthone-Omi, Inc. | Electroless nickel cobalt phosphorous composition and plating process |
| US5614003A (en) * | 1996-02-26 | 1997-03-25 | Mallory, Jr.; Glenn O. | Method for producing electroless polyalloys |
| US5804165A (en) * | 1996-07-24 | 1998-09-08 | Arnold; Michael J. | Antiplaque oral composition |
| US6183546B1 (en) | 1998-11-02 | 2001-02-06 | Mccomas Industries International | Coating compositions containing nickel and boron |
| EP2339050A1 (en) | 2001-10-24 | 2011-06-29 | Rohm and Haas Electronic Materials LLC | Stabilizers for electroless plating solutions and methods of use thereof |
| US20070243044A1 (en) * | 2006-03-29 | 2007-10-18 | Chin-Chiu Chen | Wear resistant nut |
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