US2085543A - Process for coating metals - Google Patents

Process for coating metals Download PDF

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Publication number
US2085543A
US2085543A US22651A US2265135A US2085543A US 2085543 A US2085543 A US 2085543A US 22651 A US22651 A US 22651A US 2265135 A US2265135 A US 2265135A US 2085543 A US2085543 A US 2085543A
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US
United States
Prior art keywords
tin
electrodeposit
copper
steel
nickel
Prior art date
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
Application number
US22651A
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English (en)
Inventor
Oplinger Floyd Francis
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US22651A priority Critical patent/US2085543A/en
Priority to DEP73242D priority patent/DE670403C/de
Application granted granted Critical
Publication of US2085543A publication Critical patent/US2085543A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
    • 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
    • Y10S428/9265—Special properties
    • Y10S428/927—Decorative informative
    • 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
    • Y10S428/934—Electrical process
    • Y10S428/935—Electroplating
    • 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.]
    • Y10T428/12708—Sn-base component
    • Y10T428/12722—Next to Group VIII metal-base component

Definitions

  • This invention relates to the production of rust-proof coatings on iron and steel and other metals and has for an object an improved method for applying tin and tin alloy coatings to me-
  • a further object of the invention is to provide a means for transforming a relatively dull, electroplated tin or tin alloy coating to a bright, smooth, mirror-like coating.
  • a further object is to produce 3 bright, smooth -coatings of electroplated tin on cold-rolled steel.
  • This method of pretreating cold-rolled steel to cause the finished product to be smooth and bright rather than rough and lumpy consists in first treating the steel surface with an acid to such extent that the surface is distinctly and visibly etched and fol- 0 lowing this treatment with an alkaline treatment, e. g. anodic treatment in an alkaline bath, preferably one containing an alkali metal cyanide.
  • an alkaline treatment e. g. anodic treatment in an alkaline bath, preferably one containing an alkali metal cyanide.
  • I may produce smooth, bright coatings of tin or tin alloy on cold-rolled steel and the like by first electroplating with the tin or tin alloy followed by heat treatment to the melting point of the electro- 0 deposit under substantially non-oxidizing condi- 5 compound of one or more of the following metals (Cl. 204-17l to the tin or tin alloy electroplating bath: copper, nickel, silver or a cobalt, thereby simultaneously plating out a small amount of the metal whose compound has been added to the bath together with the tin or tin alloy electrodeposit.
  • the following metals Cl. 204-17l to the tin or tin alloy electroplating bath: copper, nickel, silver or a cobalt
  • metals such as lead, cadmium, zinc and mercury are not suitable for use in the present invention.
  • the presence of such metals does no harm as a rule, but in order to obtain smooth, bright coatings of tin or tin alloy by heat-treating the electrodeposit on cold-rolled steel, I have found it essential that at least one of the metals: copper, nickel, silver or cobalt be present in a small amount in the electrodeposit.
  • I may add to an ordinary tin electroplating bath a compound of copper, nick'- el, cobalt or silver soluble in the bath and electroplate the article to be coated in the bath, whereby an electrodeposit is obtained which contains a relatively small amount of the metal whose compound is added to the bath.
  • the articleto be electroplated may be cleaned by any desired method to remove grease, dirt, oxide and the like. 'If an acid is used to remove oxide or scale, it is not necessary to continue the acid treatment to the point where visible etching occurs.
  • the electroplated article is rinsed, dried, and then heated under substantially non-oxidizing conditions to a temperature slightly above the melting point of electrodeposit.
  • substantially non-oxidizing conditions which are described in my aforesaid copending application are suitable for this step.
  • the plated article may be immersed in hot oilor molten tallow, heated in an atmosphere of substantially non-oxidizing gas such as r pose.
  • the heat-treating is not prolonged much beyond the time required to obtain complete fusion of the electrodeposit and then is preferably cooled under conditions least favorable to oxidation, e. g. by quenching in cold water or cold oil.
  • the tin electrodeposit should contain not less than about 1.4% of copper, or silver or not less than about 0.4% of nickel or cobalt. If the electrodeposit contains substantially less than these amounts, the desired result usually is not obtained and on subsequent heat-treating the coating tends to be rough or lumpy and does not appear to adhere well to the underlying surface.
  • said lower limits of copper or nickel suitable for practicing my invention are based on the specific methods of analysis which are described hereinafter in the examples given to illustrate my invention, which methods comprise an electrolytic method for determining copper and the use of dimethyl glyoxime for the determination of nickel. While generally satisfactory results may be obtained by plating out copper or nickel in the tin electrodeposit at or near to the lower limits above specified, I usually prefer to use some higher amounts of such metals to insure consistent results in extended periods of operation. Thus I prefer to operate so that the copper content of the electrodeposit is not less than about 2% by weight or, if nickel is used instead of copper, so that the nickel content in the electrodeposit is not less than about 0.5% by weight.
  • the melting point of the resulting electrodeposit obviously will depend upon the amount of copper or nickel content, the effect of large proportions of these metals being to raise the melting point of the electrodeposit.
  • the copper content of the electrodeposit should not exceed about 15% or the nickel content, if nickel is used, should not exceed about 2% by weight. By operating in this range, I have found that it is possible to obtain the desired results by heat-treating the electrodeposit under non-oxidizing conditions in a temperature range of about 230260 C.
  • Example 1 A plating solution was prepared, containing:
  • the electroplated steel cathodes were washed, dried and then heat-treated by immersing them for 10 to 30 seconds in molten tallow maintained at a temperature of about 250 C. and cooled in the air. In each trial, the resulting heat-treated plate was smooth, bright and mirror-like.
  • Example 2 A tin plating solution was made containing the following ingredients:
  • a tin plated bath was prepared having the following composition:
  • Example Cold-rolled steel was electroplated as in Example 4, except that in place of silver cyanide, sodium cobaltocyanide was added to the bath in an amount equivalent to 4.5 gms. per liter of cobalt. On heat-treating in molten tallow, a bright, smooth tin coating was obtained. The tin electrodeposit was found by an analytical method similar to that of Example 1 to contain 0.35% of cobalt. Similar trials, using smaller amounts of cobalt, produced rough, lumpy deposits on heattreating at 245 C.
  • the required concentration of the .added metal to the electroplating bath may readily be maintained by periodical additions of the metal compound at periodic intervals, e. g. once or twice daily.
  • My herein described invention is not restricted to the above described specific methods of operation which have been set forth by way of example.
  • I may electroplatc alternate layers of tin and the added metal from separate plating baths.
  • I may electroplatc a thin layer of copper or nickel on an electrodeposited tin layer and subject the resulting electrodeposit to the heat-treating operation, with satisfactory results.
  • My invention while particularly adapted for coating cold-rolled sheet steel and similar coldworked ferrous metal articles, is equally useful for plating other ferrous metal articles, e. g. hotrolled steel sheet, steel wire and the like and nonferrous metals having sufficiently high melting points to withstand the required heat-treatment, e. g. copper, brass, bronze and the like.
  • My method results in smooth, mirror-like coatings of high corrosion resistance on the various metals to which it may be applied.
  • the only preparatory treatment required prior to the electroplating step is the usual treatment for removing oxide, grease and dirt which is ordinarily used in electroplating operations.
  • a process for coating a cold rolled steel surface comprising electroplating said surface with a tin alloy consisting preponderantly of tin and containing at least one metal selected from the group consisting of copper, nickel, silver and cobalt and thereafter heating the electroplated surface under substantially non-oxidizing conditions to a temperature above the melting point of the electrodeposit and then cooling.
  • a process for coating cold-rolled steel comprising electroplating said steel from a tin bath containing not less than about 0.01 gram per liter of a dissolved copper compound and thereafter heating the electroplated steel under substantially non-oxidizing conditions to a temperature above the melting point of the electrodeposit and then cooling.
  • a process for coating cold-rolled steel comprising electroplating said steel from a tin bath containing not less than about 001 gram per liter of a dissolved nickel compound and thereafter heating the electroplated steel under substantially non-oxidizing conditions to a temperature above the melting point of the electrodeposit and then cooling.
  • a process for coating cold-rolled steel comprising electroplating said steel from an alkaline tin plating bath containing about 0.05 to 1.5 grams per liter of dissolved cuprous cyanide and thereafter heating the electroplated steel under substantially non-oxidizing conditions to a temperature above the melting point of the electrodeposit and then cooling.
  • a process for coating cold-rolled steel comprising electroplating said steel from an alkaline tin bath containing about 0.1 to 0.4 grams per liter of dissolved nickel cyanide and thereafter heating the electroplated steel under substantially non-oxidizing conditions to a temperature above the melting point of the electrodeposit and then cooling.
  • a process for producing a bright, smooth coating of tin on cold-rolled steel comprising simultaneously electroplating the surface of said steel with tin and another metal selected from the group consisting of copper, nickel, silver and cobalt in such manner that the resulting electrodeposit consists preponderantly of tin and contains an amount of said other metal not less than about 0.4% by weight when said other metal is nickel or cobalt and not less than about 1.4% when said other metal is copper or silver and thereafter heating the electroplated steel under substantially non-oxidizing conditions to a temperature above the melting point of said electrodeposit.
  • a process for producing a bright, smooth coating of tin on cold-rolled steel comprising simultaneously electroplating said steel with tin and copper in such manner that the resulting electrodeposit consists preponderantly of tin and contains not less than about 1.4% by weight of copper and thereafter heating the electroplated steel under substantially non-oxidizing conditions to a temperature above the melting point of said electrodeposit.
  • a process for producing a bright, smooth coating of tin on cold-rolled steel comprising simultaneously electroplating said steel with tin and copper in such manner that the resulting electrodeposit consists preponderantly of tin and contains about 2 to 15% by weight of copper and thereafter heating the electroplated steel under substantially non-oxidizing conditions to a temperature of about 230 to 260 C.
  • a process for producing a bright, smooth coating of tin on cold-rolled steel comprising simultaneously electroplating said steel with tin and nickel in such manner that the resulting electrodeposit consists preponderantly of tin and contains not less than about 0.4% by weight of nickel and thereafter heating the electroplated steel under substantially non-oxidizing conditions to a temperature above the melting point of said electrodeposit.
  • a process for producing a bright, smooth coating of tin 0n cold-rolled steel comprising simultaneously electroplating said steel with tin and nickel in such manner that the resulting electrodeposit consists preponderantly of tin and contains about 0.5% to 2% by weight of nickel and thereafter heating the electroplated steel under substantially non-oxidizing conditions to a temperature of about 230 to 260 C.
  • An article of manufacture comprising cold rolled steel coated with a fused metal coating which is preponderantly of tin and which contains another metal selected from the group consisting of copper, nickel, silver and cobalt, said coating containing not less than about 0.4% by weight of said otherrnetal if said other metal is nickel or cobalt and not less than about 1.4% by weight of said other metal if said other metal is copper or silver.
  • An article of manufacture comprising coldrolled steel coated with a smooth, bright, fused electrodeposit which is preponderantly of tin and which contains 1.4 to 15% by weight of copper.
  • An article of manufacture comprising a cold-rolled steel surface coated with a smooth

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
US22651A 1935-05-21 1935-05-21 Process for coating metals Expired - Lifetime US2085543A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US22651A US2085543A (en) 1935-05-21 1935-05-21 Process for coating metals
DEP73242D DE670403C (de) 1935-05-21 1936-05-23 Verfahren zur elektrolytischen Herstellung von im wesentlichen aus Zinn bestehenden UEberzuegen

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2420377A (en) * 1943-01-06 1947-05-13 Carl G Jones Method of brightening tinned strip
US2448062A (en) * 1944-09-09 1948-08-31 Westinghouse Electric Corp Transverse flux induction heating apparatus
US2459616A (en) * 1944-07-28 1949-01-18 Westinghouse Electric Corp Control apparatus for induction heating systems
US2463039A (en) * 1942-02-21 1949-03-01 Gen Motors Corp Electroplating copper containing coating
US2463412A (en) * 1942-07-25 1949-03-01 John S Nachtman Electric resistance heat-treating of electroplated coatings
US2490084A (en) * 1943-01-14 1949-12-06 Republic Steel Corp Method of controlling flow brightening of plated metal articles
US2566468A (en) * 1942-06-22 1951-09-04 United States Steel Corp Method of treating electrolytic coatings
US2576902A (en) * 1943-11-13 1951-11-27 Republic Steel Corp Method for flow brightening electrodeposited tin on tinplate
US2658866A (en) * 1949-11-22 1953-11-10 John Ireland Electrodeposition of tin-nickel alloy
US2661328A (en) * 1948-08-19 1953-12-01 Nat Steel Corp Method of flow-brightening tinplate
US3231396A (en) * 1961-08-07 1966-01-25 Dow Chemical Co Stannate immersion coating for magnesium, magnesium-dissimilar metal couples, and other metals
US3260580A (en) * 1962-11-19 1966-07-12 American Can Co Tin plate having a tin-nickel-iron alloy layer and method of making the same
US3326646A (en) * 1965-02-03 1967-06-20 Jones & Laughlin Steel Corp Tin coated steel article
US3445351A (en) * 1964-10-21 1969-05-20 Du Pont Process for plating metals
US20120223112A1 (en) * 2011-03-03 2012-09-06 Doug Campbell Golf bag buddy systems

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1069026B (de) * 1959-11-12
US2512719A (en) * 1945-09-18 1950-06-27 Du Pont Electrodeposition of tin

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2463039A (en) * 1942-02-21 1949-03-01 Gen Motors Corp Electroplating copper containing coating
US2566468A (en) * 1942-06-22 1951-09-04 United States Steel Corp Method of treating electrolytic coatings
US2463412A (en) * 1942-07-25 1949-03-01 John S Nachtman Electric resistance heat-treating of electroplated coatings
US2420377A (en) * 1943-01-06 1947-05-13 Carl G Jones Method of brightening tinned strip
US2490084A (en) * 1943-01-14 1949-12-06 Republic Steel Corp Method of controlling flow brightening of plated metal articles
US2576902A (en) * 1943-11-13 1951-11-27 Republic Steel Corp Method for flow brightening electrodeposited tin on tinplate
US2459616A (en) * 1944-07-28 1949-01-18 Westinghouse Electric Corp Control apparatus for induction heating systems
US2448062A (en) * 1944-09-09 1948-08-31 Westinghouse Electric Corp Transverse flux induction heating apparatus
US2661328A (en) * 1948-08-19 1953-12-01 Nat Steel Corp Method of flow-brightening tinplate
US2658866A (en) * 1949-11-22 1953-11-10 John Ireland Electrodeposition of tin-nickel alloy
US3231396A (en) * 1961-08-07 1966-01-25 Dow Chemical Co Stannate immersion coating for magnesium, magnesium-dissimilar metal couples, and other metals
US3260580A (en) * 1962-11-19 1966-07-12 American Can Co Tin plate having a tin-nickel-iron alloy layer and method of making the same
US3445351A (en) * 1964-10-21 1969-05-20 Du Pont Process for plating metals
US3326646A (en) * 1965-02-03 1967-06-20 Jones & Laughlin Steel Corp Tin coated steel article
US20120223112A1 (en) * 2011-03-03 2012-09-06 Doug Campbell Golf bag buddy systems

Also Published As

Publication number Publication date
DE670403C (de) 1939-01-18

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