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US3881919A - Ternary alloys - Google Patents

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Publication number
US3881919A
US3881919A US431025A US43102574A US3881919A US 3881919 A US3881919 A US 3881919A US 431025 A US431025 A US 431025A US 43102574 A US43102574 A US 43102574A US 3881919 A US3881919 A US 3881919A
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Prior art keywords
metal
chromium
alloys
cobalt
chloride
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US431025A
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Jacob Hyner
Robert A Michelson
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Whyco Chromium Co Inc
WHYCO CHROMIUM Co
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WHYCO CHROMIUM Co
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Priority to US431025A priority Critical patent/US3881919A/en
Priority to US05/533,472 priority patent/US3966564A/en
Application granted granted Critical
Publication of US3881919A publication Critical patent/US3881919A/en
Priority to US05/614,349 priority patent/USRE29239E/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin

Definitions

  • the alloys are electrodeposited from aqueous acidic baths at a temperature of about 50 85 C and current density of about 5 45 A/ft.
  • This invention relates to new and improved ternary alloys, to aqueous electrolytic baths from which the ailoys are deposited, and to a process for forming the alloys.
  • an object of the invention is to provide a new and improved alloy which not only provides a chromium-like brightness and tarnish resistance, but also provides color stability and hardness superior to that found in any of the alloying metals individually.
  • Still another object of the invention is to provide new and improved electrolytic plating baths which are easily formulated and from which ternary alloys can be efficiently deposited on a wide variety of substrates to give coatings which are hard, bright, tarnish resistant and which have good color stability.
  • Another object is to provide a new and improved process whereby tin, cobalt and a third metal are electrolytically co-deposited to form a hard, bright coating which is stable and highly resistant to tarnishing.
  • a new and improved ternary alloy consisting essentially of about 40 -]90 wt. tin, about l 50 wt. cobalt and about I 28 wt. of a third metal selected from Periodic Group II III,, or V1
  • Third metals include zinc, cadmium, indium, antimony or chromium, of which zinc, indium and chromium are preferred.
  • the third metals may be present in the alloy singly or in admixtures of two or more.
  • the plating baths of the invention are aqueous and highly acidic, and contain compounds providing stannous ions, cobaltous ions and ions of the third metal or metals to be deposited.
  • the ternary alloys are efficiently codeposited from the baths at a temperature of about 50 85C. and current density of about 5 45 A/ftF.
  • the alloys exhibit a hardness, chromium-like brightness and color stability which make them useful as coatings on a wide variety of substrates.
  • the ternary alloys of the invention are electrodeposited from highly acidic, aqueous baths of pH of about 1-3.
  • a mineral acid is utilized for this purpose, such as a hydro-halide or a sulfur acid.
  • Preferred acids are hydrochloric and fluoboric acids since such acids provide anions in common with anions of preferred compounds of the metals to be deposited, and thus promote stability of the baths and good control of electrodeposition therefrom.
  • the metals to be deposited are present in the baths as ionic compounds, the anions of the compounds and other conditions being chosen such that the compounds are substantially completely soluble in the aqueous medium. Accordingly, the compounds may be present as halides, sulfates, or otherwise but preferably the compounds will have anions common to the anions of the acid utilized to provide the high acidity. Since hydrochloric and fluoboric acids are the preferred acids, the preferred metal compounds will be the chlorides and fluoborates of the metals.
  • cobalt chloride stannous chloride zinc chloride about 20-400 g./l. about 10-100 g./l. about l0-l75 g./I.
  • cobalt chloride about [00-300 g./l. stannous fluoborate (50% solution) about 25-75 mls./l. fluoboric acid about -225 g./l.
  • Indium chloride as a substitute for zinc chloride preferably is utilized at a concentration of about 5 3S g./l. and chromium chloride as a substitute for either of the foregoing compounds is effective at a concentration of about 5 55 g./l.
  • Electrodeposition including the cell form of electrolytic arrangement and type of substrate to be coated, control of concentration and rejuvenation of the baths, are well known in the art and do not require further description.
  • the well known Hull cell may be utilized.
  • the current density preferred for efficient electrodeposition is about 5 45 A/ft.
  • the percentage of each metal in the ternary alloy will vary in direct proportion to the concentration of each metal in the plating bath. To a lesser extent the percentage of each metal in the alloy will also vary in accordance with electroplating conditions such as temperature, current density and pH. It is believed that the new alloy exists as Sn (Co, X) or (Sn, X) (Co, X) where X is the third metal.
  • the resultant ternary alloys are analogous to tin-nickel and tin-cobalt with respect to tarnish resistance, the alloys exhibit not only chromium-like brightness but also consistently good color and color stability. Moreover, while the ternary alloys resist corrosion essentially to the same extent as chromium, they have a higher resistance than chromium to strong alkali under a superimposed anoidic potential, that is, whereas chromium will dissolve if made anodic in a caustic solution, the ternary alloys of the invention are not affected. The alloys of the invention therefore are more resistant to chloride attack than chromium and will resist salt spray and salt water contact better than chromium.
  • the plating baths may contain auxiliary reagents for various purposes in accordance with the understanding in the art.
  • auxiliary reagents are ammonium chloride, gluconic acid, thiourea, fluorides such as ammonium bifluoride, sodium fluoride and potassium titanium fluoride, and various surfactants and the like such as alkyl aryl sodium sulfonate.
  • fluorides such as ammonium bifluoride, sodium fluoride and potassium titanium fluoride
  • surfactants and the like such as alkyl aryl sodium sulfonate.
  • Such reagents generally are useful in minor amounts, for example, about 0.01 to about 10 grams per liter of plating bath, to obtain their known benefits.
  • the ternary alloys may be co-deposited electrolytically upon a wide variety of substrates, including metals such as steel, brass and zinc, as well as ceramics and plastics, in accordance with techniques well known in the art for coating such substrates.
  • aqueous plating bath formulations and conditions of electrodeposition are intended as further illustration of the invention but are not necessarily limited of the scope of the invention except as set forth in the claims. All parts and percentages in these examples as well as in the foregoing specifica tion are by weight unless otherwise indicated.
  • the ternary alloy deposited has an approximate composition: tin, 40 90%; cobalt, l 50%; third metal, 1 28%.
  • Plating Conditions Temperature 60-80 C, 10 Current density 10-30 A/ft.” pH of bath 1-3 EXAMPLE 3 Composition of ueens bath Cobalt Chloride -400 g./1r Stannous Chloride 10-100 g./l. Ammonium Bifluoridc 20-400 g./l. Hydrochloric Acid (37%) 40-150 mls/l. Ammonium H droxide (28%) 10-50 rnls./l. Chromium Ch oride 5-55 g1]. 20 Plating Conditions:
  • Ammonium Hydroxide (28%) 25-150 m1s./l.
  • Fluoboric Acid 75-225 gJl.
  • Ammonium Hydroxide 28%) 25-150 mlsrll.
  • Indium Chloride 5-35 3.11.
  • Plating Conditions Temperature 50-85 C. Current density 5-45 A/f't. pH [-3 What is claimed is: l. A bright, tarnish resistant and color stable ternary alloy consisting essentially of about 40 90 wt. tin 10 50 wt. cobalt 1 28 wt. third metal wherein said third metal is antimony or a metal of Periodic Group 11,, 111,, or V1 2. A ternary alloy as in claim 1 wherein said third 5 metal is zinc, cadmium, indium, or chromium.

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

Abstract

Bright, tarnish resistant and color stable ternary alloys of about 40 - 90% of tin, about 10 - 50% cobalt and about 1 - 28% of a third metal of Periodic Group IIB, IIIA or VIB. Typical third metals are zinc, cadmium, indium, antimony or chromium. The alloys are electrodeposited from aqueous acidic baths at a temperature of about 50* - 85*C. and current density of about 5 45 A/ft.2.

Description

Hyner et a1.
May 6, 1975 TERNARY ALLOYS Inventors: Jacob Hyner; Robert A. Michelson,
both of Waterbury, Conn.
Whyeo Chromium Company Inc., Thomaston, Conn.
Filed: Jan. 7, 1974 Appl. No.: 431,025
Assignee:
US. Cl 75/175 R; 75/175 A; 75/170;
75/171, 204/43 Int. Cl. C22c 13/00 F ari of Search 75/175 R, 175 A, 134 N,
References Cited UNITED STATES PATENTS 9/1958 Klochkov.......................... 75/175 R Primary Examiner-L. Dewayne Rutledge Assistant Examiner-E. L. Weise Attorney, Agent, or FirmDelio and Montgomery [57] ABSTRACT Bright, tarnish resistant and color stable ternary alloys of about 40 90% of tin, about 10 50% cobalt and about 1 28% of a third metal of Periodic Group 11 III or VI Typical third metals are zinc, cadmium, indium, antimony or chromium. The alloys are electrodeposited from aqueous acidic baths at a temperature of about 50 85 C and current density of about 5 45 A/ft.
3 Claims, No Drawings TERNARY ALLOYS BACKGROUND OF THE INVENTION This invention relates to new and improved ternary alloys, to aqueous electrolytic baths from which the ailoys are deposited, and to a process for forming the alloys.
Various alloys have been developed in efforts to duplicate the superior color of chromium and alloys containing substantial amounts of chromium, while also providing the corrosion resistance and tarnish resistance required when the alloy is to be used as a protective coating. Accordingly, the prior art teaches the addition of brightening agents to plating baths for the electro-deposition of tin-nickel binary alloys, as in US. Pat. No. 3,141,836 Seyb et al, or the careful control of plating conditions, also in the deposition of nickeltin binary allows, such as the highly acidic baths in US. Pat. No. 2,926,] 24 Taylor et al. In another approach cobalt-tin binary alloys have been studied with respect to close similarities in corrosion resistance to nickel-tin alloys. Clarke et al, An Electrodeposited Bright Tin- Cobalt lntermetallic Compound, CoSn, Transactions of the Institute of Metal Finishing, 1972, Volume 50.
Despite the usefulness of such alloys from the standpoint of tarnish and corrosion resistance, those of such alloys which initially exhibited brightness similar to that of chromium did not maintain the good color. Moreover, results in obtaining hardness, brightness, tarnish resistance and color stability have not been consistent. Such properties tend to be overly sensitive to specific process conditions and therefore are difficult to reproduce on a commercial scale.
OBJECTS AND SUMMARY Accordingly, an object of the invention is to provide a new and improved alloy which not only provides a chromium-like brightness and tarnish resistance, but also provides color stability and hardness superior to that found in any of the alloying metals individually.
Still another object of the invention is to provide new and improved electrolytic plating baths which are easily formulated and from which ternary alloys can be efficiently deposited on a wide variety of substrates to give coatings which are hard, bright, tarnish resistant and which have good color stability.
Another object is to provide a new and improved process whereby tin, cobalt and a third metal are electrolytically co-deposited to form a hard, bright coating which is stable and highly resistant to tarnishing.
These and other objects, features and advantages of the invention will be apparent from the description which follows.
In summary outline, the foregoing and other objects are achieved in a new and improved ternary alloy consisting essentially of about 40 -]90 wt. tin, about l 50 wt. cobalt and about I 28 wt. of a third metal selected from Periodic Group II III,, or V1 Third metals include zinc, cadmium, indium, antimony or chromium, of which zinc, indium and chromium are preferred. The third metals may be present in the alloy singly or in admixtures of two or more. The plating baths of the invention are aqueous and highly acidic, and contain compounds providing stannous ions, cobaltous ions and ions of the third metal or metals to be deposited. The ternary alloys are efficiently codeposited from the baths at a temperature of about 50 85C. and current density of about 5 45 A/ftF. In addition to the tarnish resistance expected in alloys containing tin and cobalt, the alloys exhibit a hardness, chromium-like brightness and color stability which make them useful as coatings on a wide variety of substrates.
DESCRIPTION OF THE PREFERRED EMBODIMENTS The ternary alloys of the invention are electrodeposited from highly acidic, aqueous baths of pH of about 1-3. A mineral acid is utilized for this purpose, such as a hydro-halide or a sulfur acid. Preferred acids are hydrochloric and fluoboric acids since such acids provide anions in common with anions of preferred compounds of the metals to be deposited, and thus promote stability of the baths and good control of electrodeposition therefrom.
The metals to be deposited are present in the baths as ionic compounds, the anions of the compounds and other conditions being chosen such that the compounds are substantially completely soluble in the aqueous medium. Accordingly, the compounds may be present as halides, sulfates, or otherwise but preferably the compounds will have anions common to the anions of the acid utilized to provide the high acidity. Since hydrochloric and fluoboric acids are the preferred acids, the preferred metal compounds will be the chlorides and fluoborates of the metals.
The metal compounds may be dispersed and dissolved in the aqueous medium in any suitable manner with heating and agitation, as needed. Sequence of admixture is not critical although the usual precautions with highly acidic solutions should be exercised. However, dispersion and electroplating are each benefited by somewhat elevated temperature of the bath, of the order of about 50 85C.
As chlorides the following ranges of concentrations of the metal compounds in the baths are effective:
cobalt chloride stannous chloride zinc chloride about 20-400 g./l. about 10-100 g./l. about l0-l75 g./I.
cobalt chloride about [00-300 g./l. stannous fluoborate (50% solution) about 25-75 mls./l. fluoboric acid about -225 g./l.
about 25-150 mls./l. about l0-135 g./l.
ammonium hydroxide (28% solution) zinc chloride Indium chloride as a substitute for zinc chloride preferably is utilized at a concentration of about 5 3S g./l. and chromium chloride as a substitute for either of the foregoing compounds is effective at a concentration of about 5 55 g./l.
Other conditions of electrodeposition, including the cell form of electrolytic arrangement and type of substrate to be coated, control of concentration and rejuvenation of the baths, are well known in the art and do not require further description. For example, the well known Hull cell may be utilized. The current density preferred for efficient electrodeposition is about 5 45 A/ft.
Generally, the percentage of each metal in the ternary alloy will vary in direct proportion to the concentration of each metal in the plating bath. To a lesser extent the percentage of each metal in the alloy will also vary in accordance with electroplating conditions such as temperature, current density and pH. It is believed that the new alloy exists as Sn (Co, X) or (Sn, X) (Co, X) where X is the third metal.
While the resultant ternary alloys are analogous to tin-nickel and tin-cobalt with respect to tarnish resistance, the alloys exhibit not only chromium-like brightness but also consistently good color and color stability. Moreover, while the ternary alloys resist corrosion essentially to the same extent as chromium, they have a higher resistance than chromium to strong alkali under a superimposed anoidic potential, that is, whereas chromium will dissolve if made anodic in a caustic solution, the ternary alloys of the invention are not affected. The alloys of the invention therefore are more resistant to chloride attack than chromium and will resist salt spray and salt water contact better than chromium.
The plating baths may contain auxiliary reagents for various purposes in accordance with the understanding in the art. Among such auxiliary reagents are ammonium chloride, gluconic acid, thiourea, fluorides such as ammonium bifluoride, sodium fluoride and potassium titanium fluoride, and various surfactants and the like such as alkyl aryl sodium sulfonate. Such reagents generally are useful in minor amounts, for example, about 0.01 to about 10 grams per liter of plating bath, to obtain their known benefits.
The ternary alloys may be co-deposited electrolytically upon a wide variety of substrates, including metals such as steel, brass and zinc, as well as ceramics and plastics, in accordance with techniques well known in the art for coating such substrates.
The following examples of aqueous plating bath formulations and conditions of electrodeposition are intended as further illustration of the invention but are not necessarily limited of the scope of the invention except as set forth in the claims. All parts and percentages in these examples as well as in the foregoing specifica tion are by weight unless otherwise indicated. In each example the ternary alloy deposited has an approximate composition: tin, 40 90%; cobalt, l 50%; third metal, 1 28%.
EXAMPLE 1 CornEsition of ageuous bath Cobalt Chloride 20-400 gJl. Stannous Chloride 10-100 gjl. Ammonium Bifluoride 20-400 g./l. Hydrochloric Acid (37%) 40-150 mls./l. Ammonium Hydroxide (28%) 10-50 m1s./l. Zinc Chloride 15-175 g./l.
Plating Conditions: Temperature of bath (mo-80 C. Current density 10-30 A/lt. pH of bath l-3 EXAMPLE 2 Commsition of ag ueous bath 5 Cobalt Chloride 20-400 gvll. Stannous Chloride -100 g./l. Ammonium Bifluoride 20-400 g./l. Hydrochloric Acid (37%) 40-150 mls./l. Ammonium H droxide (28%) 10-50 mls./1. lndium Chlori e 5-35 g./l.
Plating Conditions: Temperature 60-80 C, 10 Current density 10-30 A/ft." pH of bath 1-3 EXAMPLE 3 Composition of ueens bath Cobalt Chloride -400 g./1r Stannous Chloride 10-100 g./l. Ammonium Bifluoridc 20-400 g./l. Hydrochloric Acid (37%) 40-150 mls/l. Ammonium H droxide (28%) 10-50 rnls./l. Chromium Ch oride 5-55 g1]. 20 Plating Conditions:
Temperature (SO-80 C. Current density 10-30 A/ft. pH of bath [-3 EXAMPLE 4 Com sition of a q' ueous bath Cobalt Chloride 100-300 r/l. Stannous Fluoborate (50%) 25-75 mfs/l. Fluoboric Acid 75-225 gfl. Ammonium Hydroxide (28%) 25-150 m/s./l. 30 Zinc Chloride l0-135 g./l.
Plating Conditions: Temperature 50-85 C Current density 5-45 A/lt. pH [-3 EXAMPLE 5 Comggitlon of g ueous bath Cobalt Chloride 100-300 ./1. Stannous Fluoborate (50%) 25-75 m s.(l. Fluoboric Acid 75-225 g./.
Ammonium Hydroxide (28%) 25-150 m1s./l. Chromium Ch oride 10-75 g./l.
Hating Conditions: Temperature 50-85 C. Current density 5-45 A/lt. pH |-3 EXAMPLE 6 Commgition of gueous bath Cobalt Chloride 100-300 .ll. Stannous Fluoborate (50%) 25-75 m sJl.
Fluoboric Acid 75-225 gJl. Ammonium Hydroxide (28%) 25-150 mlsrll. Indium Chloride 5-35 3.11.
Plating Conditions: Temperature 50-85 C. Current density 5-45 A/f't. pH [-3 What is claimed is: l. A bright, tarnish resistant and color stable ternary alloy consisting essentially of about 40 90 wt. tin 10 50 wt. cobalt 1 28 wt. third metal wherein said third metal is antimony or a metal of Periodic Group 11,, 111,, or V1 2. A ternary alloy as in claim 1 wherein said third 5 metal is zinc, cadmium, indium, or chromium.
3. A ternary alloy as in claim I wherein said third metal is zinc, indium or chromium.
1 i 1 I I.

Claims (3)

1. A BRIGHT, TARNISH RESISTANT AND COLOR STABLE TERNARY ALLOY CONSISTING ESSENTIALLY OF ABOUT 40-90 WT.% TIN 10-50 WT.% COBALT 1-28 WT.% THIRD METAL WHEREIN SAID THIRD METAL IS ANTIMONY OR A METAL OF PERIODIC GROUP IIB, III$ OR VIB.
2. A ternary alloy as in claim 1 wherein said third metal is zinc, cadmium, indium, or chromium.
3. A ternary alloy as in claim 1 wherein said third metal is zinc, indium or chromium.
US431025A 1974-01-07 1974-01-07 Ternary alloys Expired - Lifetime US3881919A (en)

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US05/533,472 US3966564A (en) 1974-01-07 1974-12-17 Method of electrodepositing an alloy of tin, cobalt and a third metal and electrolyte therefor
US05/614,349 USRE29239E (en) 1974-01-07 1975-09-17 Ternary alloys

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4029556A (en) * 1975-10-22 1977-06-14 Emlee Monaco Plating bath and method of plating therewith
US4035249A (en) * 1975-06-10 1977-07-12 Oxy Metal Industries Corporation Electrode position of tin-containing alloys and bath therefor
US4299671A (en) * 1980-06-13 1981-11-10 Hooker Chemicals & Plastics Corp. Bath composition and method for electrodepositing cobalt-zinc alloys simulating a chromium plating
US4795682A (en) * 1986-07-19 1989-01-03 Ae Plc Tin-cobalt bearing overlay alloys
US5333550A (en) * 1993-07-06 1994-08-02 Teledyne Mccormick Selph Tin alloy sheath material for explosive-pyrotechnic linear products
US5501154A (en) * 1993-07-06 1996-03-26 Teledyne Industries, Inc. Substantially lead-free tin alloy sheath material for explosive-pyrotechnic linear products
US5766776A (en) * 1994-12-07 1998-06-16 Wieland-Werke Ag Strip shaped or wire-shaped compound material
WO2001002627A1 (en) * 1999-07-06 2001-01-11 Dunigan, Frank, C. Method and electroplating solution for plating antimony and antimony alloy coatings
WO2002022913A3 (en) * 2000-09-16 2002-07-25 Degussa Galvanotechnik Gmbh Ternary tin zinc alloy, electroplating solutions and galvanic method for producing ternary tin zinc alloy coatings
US20040055495A1 (en) * 2002-04-23 2004-03-25 Hannagan Harold W. Tin alloy sheathed explosive device

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2853382A (en) * 1957-07-24 1958-09-23 John V Klochkov Alloy compositions

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2853382A (en) * 1957-07-24 1958-09-23 John V Klochkov Alloy compositions

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4035249A (en) * 1975-06-10 1977-07-12 Oxy Metal Industries Corporation Electrode position of tin-containing alloys and bath therefor
US4029556A (en) * 1975-10-22 1977-06-14 Emlee Monaco Plating bath and method of plating therewith
US4299671A (en) * 1980-06-13 1981-11-10 Hooker Chemicals & Plastics Corp. Bath composition and method for electrodepositing cobalt-zinc alloys simulating a chromium plating
US4795682A (en) * 1986-07-19 1989-01-03 Ae Plc Tin-cobalt bearing overlay alloys
US5333550A (en) * 1993-07-06 1994-08-02 Teledyne Mccormick Selph Tin alloy sheath material for explosive-pyrotechnic linear products
US5501154A (en) * 1993-07-06 1996-03-26 Teledyne Industries, Inc. Substantially lead-free tin alloy sheath material for explosive-pyrotechnic linear products
US5766776A (en) * 1994-12-07 1998-06-16 Wieland-Werke Ag Strip shaped or wire-shaped compound material
WO2001002627A1 (en) * 1999-07-06 2001-01-11 Dunigan, Frank, C. Method and electroplating solution for plating antimony and antimony alloy coatings
US6409906B1 (en) 1999-07-06 2002-06-25 Frank C. Danigan Electroplating solution for plating antimony and antimony alloy coatings
WO2002022913A3 (en) * 2000-09-16 2002-07-25 Degussa Galvanotechnik Gmbh Ternary tin zinc alloy, electroplating solutions and galvanic method for producing ternary tin zinc alloy coatings
US20040091385A1 (en) * 2000-09-16 2004-05-13 Klaus Leyendecker Ternary tin zinc alloy, electroplating solutions and galvanic method for producing ternary tin zinc alloy coatings
US20040055495A1 (en) * 2002-04-23 2004-03-25 Hannagan Harold W. Tin alloy sheathed explosive device

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