US2884350A - Solderable zinc alloy coating - Google Patents

Solderable zinc alloy coating Download PDF

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Publication number
US2884350A
US2884350A US555782A US55578255A US2884350A US 2884350 A US2884350 A US 2884350A US 555782 A US555782 A US 555782A US 55578255 A US55578255 A US 55578255A US 2884350 A US2884350 A US 2884350A
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United States
Prior art keywords
zinc
solderable
tin
percent
coating
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US555782A
Inventor
Edward B Saubestre
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GTE Sylvania Inc
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Sylvania Electric Products Inc
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Publication date
Application filed by Sylvania Electric Products Inc filed Critical Sylvania Electric Products Inc
Priority to US555782A priority Critical patent/US2884350A/en
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Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/53—Treatment of zinc or alloys based thereon
    • 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.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12583—Component contains compound of adjacent metal
    • Y10T428/1259—Oxide

Definitions

  • the present invention relates to the treatment of metal surfaces to inhibit finger staining and to improve corrosion resistance while retaining a readily solderable surface.
  • the present invention relates to dips for solderable zinc-tin alloys, and to improved dipping processes for said alloys which provide a solderable, rust resistant coating which is not relatively prone to finger staining and is of attractive appearance.
  • Dipping solutions which are suitable for processing articles of zinc-tin alloy clad either by electrodeposition or other means are solutions of strong acids which are oxidizing. Excellent results have been obtained with Patented Apr. 28, 1959 solutions consisting essentially of nitric acid, sulfuric acid and mineral acid-hydrogen peroxide mixtures.
  • the strength of the oxidizing acid solution and the immersion time is selected to convert the normally white, matte surface of the solderable zinc-tin alloy into an oxidized film; such a film, although protective, does not interfere with the solderability of the coating and has a pleasing gray color.
  • Example.-A base metal clad with solderable zinc-tin alloy having approximately percent zinc and 10 percent tin was immersed in a dip of 1 percent by weight of nitric acid for a period of between 20 seconds to one minute in which time a gray oxidized coating was formed on the exposed surfaces of the article.
  • the dipping process was inhibited by first rinsing in cold water followed by rinsing in hot water and drying.
  • the gray oxidized coating suppressed finger staining while not interfering with solderability.
  • the residues left from the original zinc-tin alloy plating were removed by the dipping process.
  • a process for treating a solderable zinc-tin alloy containing between 75 and percent zinc and between 25 and 5 percent tin and normally having a white matte surface including the steps of subjecting said surface to the action of an oxidizing acid solution of a strength and for a duration to convert said white matte surface into an oxidized film, and removing said surface from the action of said solution before appreciable buildup of said oxidized film.
  • a process for treating a solderable zinc-tin alloy containing between 75 and 95 percent zinc and between 25 and 5 percent tin and normally having a white matte surface including the steps of subjecting said surface to the action of an oxidizing acid solution selected from the group consisting of nitric acid, sulfuric acid and mineral acid-hydrogen peroxide mixtures and of a strength and for a duration to convert said white matte surface into an oxidized film, and removing said surface from the action of said solution before appreciable building of said oxidized film.
  • an oxidizing acid solution selected from the group consisting of nitric acid, sulfuric acid and mineral acid-hydrogen peroxide mixtures and of a strength and for a duration to convert said white matte surface into an oxidized film
  • An article of an electrodeposited zinc-tin alloy containing 75 to 95 percent zinc and 25 to 5 percent tin and having a gray oxidized solderable film of uniform thickness on its surface which is resistant to finger straining.
  • a base metal having a coating of a solderable zinc-tin alloy containing 75 to 95 percent zinc and 25 to 5 percent tin, the surfaces of said coating having an oxidized film of a thickness to preclude finger staining without affecting solderability, said film being gray in color, uniform in thickness and solderable.

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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)
  • Electroplating Methods And Accessories (AREA)

Description

United States Patent filice SOLDERABLE zlNc ALLOY COATING Edward B. Saubestre, Elmhurst, N.Y., assignor to Sylvania Electric Products Inc., a corporation of Massachusetts No Drawing. Application December 28, 1955 Serial No. 555,782
6 Claims. (Cl. 148-614) The present invention relates to the treatment of metal surfaces to inhibit finger staining and to improve corrosion resistance while retaining a readily solderable surface. In particular, the present invention relates to dips for solderable zinc-tin alloys, and to improved dipping processes for said alloys which provide a solderable, rust resistant coating which is not relatively prone to finger staining and is of attractive appearance.
In application Serial No. 526,860, filed August 8, 1955, in the name of the inventor herein and assigned to the assignee of the present invention, there is described improved plating methods and baths for obtaining a solderable zinc-tin alloy containing between 75 and 95 percent zinc and between 25 and percent tin; This alloy finds many applications in the electronics industry and is an excellent substitute for the scarce and rather expensive cadmium. Solder-able zinc-tin alloys, electrodeposited according to said application, have a white matte finish which is prone to finger staining.
Broadly, it is an object of the present invention to provide an improved dip and dipping process for solderable zinc-tin alloys which provides a finish which is relatively passive to finger staining and which may be handled without danger of adversely altering the appearance of the alloy. Specifically, it is within the contemplation of the invention to provide treatment methods and baths which render electro-deposited zinc-tin alloys less prone to finger staining and white salt formation, Without aifecting the solderability of the alloy.
I have found that the treatment of such electrodeposited zinc-tin alloys with acid oxidizing solutions converts the normally white matte surface of the alloys to an oxidized surface without affecting the important property of solderability. The oxidized surface has a gray finish of attractive appearance which is resistant to corrosion and tarnishing. Known bright dips for zinc electro-deposited coatings, such as those of the nitric acid type, are not effective when foreign metals are present in the zinc bright dip solution; accordingly, known treatment methods for zinc were not expected to find application to the processing of zinc-tin alloys. However, the reverse was found to be true. Further, the desirable surface properties must be broughtabout in a manner consistent with the requirement that the solderability of the zinc-tin alloy be preserved. Thus, conventional chromate conversion coatings cannot be employed since such chromate films interfere with solderability, particularly as the thickness of the chromate coating increases.
Dipping solutions which are suitable for processing articles of zinc-tin alloy clad either by electrodeposition or other means are solutions of strong acids which are oxidizing. Excellent results have been obtained with Patented Apr. 28, 1959 solutions consisting essentially of nitric acid, sulfuric acid and mineral acid-hydrogen peroxide mixtures. The strength of the oxidizing acid solution and the immersion time is selected to convert the normally white, matte surface of the solderable zinc-tin alloy into an oxidized film; such a film, although protective, does not interfere with the solderability of the coating and has a pleasing gray color.
The following specific example is given, without limitation, to more completely explain my invention:
Example.-A base metal clad with solderable zinc-tin alloy having approximately percent zinc and 10 percent tin was immersed in a dip of 1 percent by weight of nitric acid for a period of between 20 seconds to one minute in which time a gray oxidized coating was formed on the exposed surfaces of the article. The dipping process was inhibited by first rinsing in cold water followed by rinsing in hot water and drying. The gray oxidized coating suppressed finger staining while not interfering with solderability. The residues left from the original zinc-tin alloy plating were removed by the dipping process.
A latitude of substitution and modification is intended in the foregoing disclosure; and in some instances some features of the invention will be used without a corresponding use of other features.
What I claim is:
1. A process for treating a solderable zinc-tin alloy containing between 75 and percent zinc and between 25 and 5 percent tin and normally having a white matte surface including the steps of subjecting said surface to the action of an oxidizing acid solution of a strength and for a duration to convert said white matte surface into an oxidized film, and removing said surface from the action of said solution before appreciable buildup of said oxidized film.
2. A process for treating a solderable zinc-tin alloy containing between 75 and 95 percent zinc and between 25 and 5 percent tin and normally having a white matte surface including the steps of subjecting said surface to the action of an oxidizing acid solution selected from the group consisting of nitric acid, sulfuric acid and mineral acid-hydrogen peroxide mixtures and of a strength and for a duration to convert said white matte surface into an oxidized film, and removing said surface from the action of said solution before appreciable building of said oxidized film.
3. An article of an electrodeposited zinc-tin alloy containing 75 to 95 percent zinc and 25 to 5 percent tin and having a thin oxidized film on its surface, said film being gray in color, uniform in thickness and solderable.
4. An article of an electrodeposited zinc-tin alloy containing 75 to 95 percent zinc and 25 to 5 percent tin and having a gray oxidized solderable film of uniform thickness on its surface which is resistant to finger straining.
5. A base metal having a coating of a solderable zinc-tin alloy containing 75 to 95 percent zinc and 25 to 5 percent tin, the surfaces of said coating having an oxidized film of a thickness to preclude finger staining without affecting solderability, said film being gray in color, uniform in thickness and solderable.
6. The method of treating an electrolytically deposited layer of an alloy of zinc and tin, said alloy containing between 75 and 95% zinc and between 25 and 5% tin, the layer having a solderable surface which includes 3 l 5 4 I the step of immersing the surface in a solution of nitric 2,035,380 Wilhelm Mar. 24, 1936 acid so as to form a uniform, gray, oxidized coating 2,154,451 Hull Apr. 18, 1939 over the surface, the coating having the property of 2,154,469 Oplinger Apr. 18, 1939 repressing finger staining and being solderable, remov- 2,276,353 Thompson Mar. 17, 1942 ing the surface from the solution and washing the nitric 5 2,461,228 Miles Feb. 8, 1949 acid solution off from the removed surface. 2,559,812 Watson July 10, 1951 References Cited in the file of this patent B brk G lOTHER SE Z Z & FN S a 1 avam'zing, r e ition, pon UNITED STATES PATENTS 10 Ltd.; 22 Henrietta St., London W0. 2 1950 (pages 122,716 Fobes Jan. 16, 1872 112 and 11 relied 1,923,502 Prier Aug. 22, 1933 Patent No, 2,884,350
April 28, 1959 Edward B. Saubestre It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 2,, line 57, for. "straining" read staining (SEAL) Attest:
KARL Ho AXLINE Attesting Oflicer ROBERT C. WATSON Commissioner of Patents

Claims (1)

1. A PROCESS FOR TREATING A SOLDERABLE ZINC-TIN ALLOY CONTAINING BETWEEN 75 AND 95 PERCENT ZINC AND BETWEEN 25 AND 5 PERCENT TIN AND NORMALLY HAVING A WHITE MATTE SURFACE INCLUDING THE STEPS OF SUBJECTING SAID SURFACE AND THE ACTION OF AN OXIDIZING ACID SOLUTION OF A STRENGTH AND FOR A DURATION TO CONVERT SAID WHITE MATTE SURFACE FROM THE AN OXIDIZED FILM, AND REMOVING SAID SURFACE FROM THE ACTION OF SAID SOLUTION BEFORE APPRECIABLE BUILDUP OF SAID OXIDIZED FILM.
US555782A 1955-12-28 1955-12-28 Solderable zinc alloy coating Expired - Lifetime US2884350A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3418174A (en) * 1964-08-20 1968-12-24 United States Steel Corp Method of making gal vannealed ferrous metal of improved solderability
DE2757592A1 (en) * 1977-12-23 1979-07-05 Rheinisches Zinkwalzwerk Gmbh METHOD OF SURFACE TREATMENT OF MOLDED BODIES MADE OF ZINC OR ZINC ALLOYS
US4957594A (en) * 1988-02-19 1990-09-18 Nippon Steel Corporation Process for producing a zinc or zinc alloy coated steel sheet having excellent spot weldability
US5695822A (en) * 1993-04-05 1997-12-09 The Louis Berkman Company Method for coating a metal strip
US6080497A (en) * 1992-03-27 2000-06-27 The Louis Berkman Company Corrosion-resistant coated copper metal and method for making the same
US6652990B2 (en) 1992-03-27 2003-11-25 The Louis Berkman Company Corrosion-resistant coated metal and method for making the same
US6794060B2 (en) 1992-03-27 2004-09-21 The Louis Berkman Company Corrosion-resistant coated metal and method for making the same
US20040214029A1 (en) * 1992-03-27 2004-10-28 The Louis Berkman Company, An Ohio Corporation Corrosion-resistant coated copper and method for making the same
US20070169605A1 (en) * 2006-01-23 2007-07-26 Szymanski David A Components having sharp edge made of sintered particulate material
US20180021896A1 (en) * 2016-07-25 2018-01-25 National Cheng Kung University Lead-free solder composition

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US122716A (en) * 1872-01-16 Improvement in alloys for lining water-coolers, tanks
US1923502A (en) * 1930-04-24 1933-08-22 Prier Pierre Process and product for protecting aluminium, magnesium, zing and their alloys against corrosion
US2035380A (en) * 1933-05-13 1936-03-24 New Jersey Zinc Co Method of coating zinc or cadmium base metals
US2154451A (en) * 1934-12-17 1939-04-18 Du Pont Bright dip
US2154469A (en) * 1934-12-17 1939-04-18 Du Pont Bright dip
US2276353A (en) * 1935-09-28 1942-03-17 Parker Rust Proof Co Process of coating
US2461228A (en) * 1949-02-08 Donald lee miles
US2559812A (en) * 1949-01-25 1951-07-10 Tennessee Coal Iron And Railro Solution and method for coating zinc surfaces

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US122716A (en) * 1872-01-16 Improvement in alloys for lining water-coolers, tanks
US2461228A (en) * 1949-02-08 Donald lee miles
US1923502A (en) * 1930-04-24 1933-08-22 Prier Pierre Process and product for protecting aluminium, magnesium, zing and their alloys against corrosion
US2035380A (en) * 1933-05-13 1936-03-24 New Jersey Zinc Co Method of coating zinc or cadmium base metals
US2154451A (en) * 1934-12-17 1939-04-18 Du Pont Bright dip
US2154469A (en) * 1934-12-17 1939-04-18 Du Pont Bright dip
US2276353A (en) * 1935-09-28 1942-03-17 Parker Rust Proof Co Process of coating
US2559812A (en) * 1949-01-25 1951-07-10 Tennessee Coal Iron And Railro Solution and method for coating zinc surfaces

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3418174A (en) * 1964-08-20 1968-12-24 United States Steel Corp Method of making gal vannealed ferrous metal of improved solderability
DE2757592A1 (en) * 1977-12-23 1979-07-05 Rheinisches Zinkwalzwerk Gmbh METHOD OF SURFACE TREATMENT OF MOLDED BODIES MADE OF ZINC OR ZINC ALLOYS
FR2412622A1 (en) * 1977-12-23 1979-07-20 Rheinisches Zinkwalzwerk Gmbh SURFACE TREATMENT PROCESS OF BODIES SHAPED IN ZINC OR A ZINC ALLOY AND PRODUCTS OBTAINED BY THIS PROCESS
US4957594A (en) * 1988-02-19 1990-09-18 Nippon Steel Corporation Process for producing a zinc or zinc alloy coated steel sheet having excellent spot weldability
US6861159B2 (en) 1992-03-27 2005-03-01 The Louis Berkman Company Corrosion-resistant coated copper and method for making the same
US6858322B2 (en) 1992-03-27 2005-02-22 The Louis Berkman Company Corrosion-resistant fuel tank
US6652990B2 (en) 1992-03-27 2003-11-25 The Louis Berkman Company Corrosion-resistant coated metal and method for making the same
US6794060B2 (en) 1992-03-27 2004-09-21 The Louis Berkman Company Corrosion-resistant coated metal and method for making the same
US20040214029A1 (en) * 1992-03-27 2004-10-28 The Louis Berkman Company, An Ohio Corporation Corrosion-resistant coated copper and method for making the same
US20040213916A1 (en) * 1992-03-27 2004-10-28 The Louis Berkman Company, A Corporation Of Ohio Corrosion-resistant fuel tank
US6811891B2 (en) 1992-03-27 2004-11-02 The Louis Berkman Company Corrosion-resistant coated metal and method for making the same
US6080497A (en) * 1992-03-27 2000-06-27 The Louis Berkman Company Corrosion-resistant coated copper metal and method for making the same
US7575647B2 (en) 1992-03-27 2009-08-18 The Louis Berkman Co. Corrosion-resistant fuel tank
US7045221B2 (en) 1992-03-27 2006-05-16 The Louis Berkman Company Corrosion-resistant coated copper and method for making the same
US20070023111A1 (en) * 1992-03-27 2007-02-01 The Louis Berkman Company, A Corporation Of Ohio Corrosion-resistant fuel tank
US20070104975A1 (en) * 1992-03-27 2007-05-10 The Louis Berkman Company Corrosion-resistant coated copper and method for making the same
US5695822A (en) * 1993-04-05 1997-12-09 The Louis Berkman Company Method for coating a metal strip
US20070169605A1 (en) * 2006-01-23 2007-07-26 Szymanski David A Components having sharp edge made of sintered particulate material
US20180021896A1 (en) * 2016-07-25 2018-01-25 National Cheng Kung University Lead-free solder composition

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