US3420754A - Electroplating a ductile zinc-nickel alloy onto strip steel - Google Patents

Electroplating a ductile zinc-nickel alloy onto strip steel Download PDF

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Publication number
US3420754A
US3420754A US439268A US3420754DA US3420754A US 3420754 A US3420754 A US 3420754A US 439268 A US439268 A US 439268A US 3420754D A US3420754D A US 3420754DA US 3420754 A US3420754 A US 3420754A
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zinc
nickel
electroplating
plating
bath
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US439268A
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Edward J Roehl
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Pittsburgh Steel Co
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Pittsburgh Steel Co
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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
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
    • 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.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y10T428/12799—Next to Fe-base component [e.g., galvanized]

Definitions

  • the invention is concerned with the electrodeposition on steel strip of a Zinc-nickel alloy plating containing nickel in a predetermined range of 6.5 to 9.5%, for the purpose of providing a coating having an expansive internal stress of about 500-1400 p.s.i., whereby a high ductility and low internal stress enables the plated strip to be subjected to cutting, bending, stamping or forming operations without cracking or breaking of the plating. At the same time, superior corrosion-resistant properties for the plating are obtained.
  • This invention relates generally to the electrodeposition of alloys from acid plating baths, but has reference more particularly to the electrodeposition of alloys or co-deposits of zinc and nickel, the composition of which is controlled within specific, fairly critical, limits or ranges for the purpose of obtaining new and desirable physical properties for specific, useful, commercial applications.
  • Zinc is one of the most widely used metallic coatings for steel surfaces to protect such surfaces from corrosion, the principal methods of applying such coatings being hot dipping and electroplating.
  • the hot dipping method produces thick coatings of a thickness of 0.001 inch or more, which are alloyed to the surfaces of the steel. These intersurface alloys are brittle and not suitable for drawing and forming operations.
  • Electroplating produces thinner coatings, of the order of a few ten-thousandths of an inch in thickness, with no alloy intersurface layer between the base metal coating, and hence can be formed and drawn satisfactorily.
  • Zinc has been electroplated on steel surfaces from acid plating baths for many years for the purpose of providing protection of the steel surface for commercial uses.
  • commercial materials so protected is continuous steel strip which, after being plated, is fabricated into useful articles of manufacture by cutting, stamping, drawing and forming operations.
  • the electroplated zinc coating possesses minimum internal stress and maximum ductility.
  • these conditions or requirements have been best met by eliminating impurities from the plating bath, so as to deposit zinc of the highest purity.
  • FIG. 1 shows that electrodeposited alloys within a narrow range of 6.59.5% nickel, with the remainder zinc, and preferably within a range of 79% nickel, with the remainder zinc, have an expansive internal stress of about 500-1400 p.s.i., as compared with an expansive internal stress of about 500 p.s.i. for pure electroplated zinc, while electroplated nickel alloys containing over 9.5 nickel have a rapidly rising contractile internal stress, with corresponding loss of ductility, which accounts for the great difficulty encountered in working or forming products plated with them, as hereinbefore referred to.
  • FIG. 1 further indicates that a preferred alloy or composition within the selected range, and which has a maximum expansive internal stress of about 1400 p.s.i., is one consisting of about 92% zinc and about 8% nickel.
  • Internal residual stress is stress present in a body that is free of external forces or thermal gradients.
  • coated material made in accordance with my invention having a coating of the composition described above, can be bent, stamped, drawn, formed, or otherwise Worked into finished articles or products without cracking or damaging the coating in any manner.
  • FIG. 2 of the accompanying drawings the results of salt spray tests on flat specimens of coated strip steel, coated respectively with the aforesaid 92%-8% nickel alloy, pure electrolytic zinc, and hot-dipped zinc, are depicted graphically
  • FIG. 3 of the accompanying drawing the results of the same salt spray tests, on similar specimens, after forming, are depicted graphically.
  • the 92% zinc-8% nickel alloy coating is seen to be from three to four times as corrosionresistant as the electrolytic zinc and hot-dipped zinc coatings, and can therefore be used in thickness of only onethird to one-fourth those of pure zinc, for corresponding degrees of protection, thereby effecting considerable economies.
  • the invention therefore, simply stated, comprises plating or electrodepositing a highly corrosive-resistant alloy of zinc and nickel, of minimum internal stress and maximum ductility, on steel surfaces, said alloy having a carefully controlled composition within narrow critical limits achieved by careful control of the plating bath composition and operating conditions, thus producing a new and useful product at low cost.
  • the important factor in plating bath composition and control is to maintain the ratio between the concentration of zinc metal in solution and the concentration of nickel metal in solution with respect to total metal concentration and operating conditions so that the composition of the alloy plated therefrom will be as close to 92% zinc and 8% nickel as possible, and preferably within the limits of 93-91% zinc and 79% nickel, but never less than 90.5% zinc or more than 9.5% nickel.
  • this objective can best be accomplished by maintaining the zinc metal concentration in the bath at between 8 and 10 ounces per gallon, with the nickel metal concentration at between 4 and 5 ounces per gallon, and the ratio of zinc metal concentration to nickel metal concentration as close as 2:1 as possible.
  • anionic composition of the plating bath is not critical, hence any water-soluble salts of zinc and nickel commonly used in plating baths and compatible therewith can be used alone or in any desirable combination, although I prefer to use a chloride bath because of its higher conductivity and therefore greater productivity.
  • wetting agents which lower the surface tension of the bath may be added thereto if desired to eliminate pitting, if encountered, and to improve the uniformity of deposit appearance.
  • the identity of the wetting agents chosen is not important, although they must, of course, be compatible with the bath and cause no deleterious effects.
  • Some of the wetting agents used in commercial nickel plating have been found to be satisfactory, as for example, sulfated or sulfonated lauryl alcohol, one of the commonest so used. Others which produce less foam may be preferred, but the selection of such wetting agents most suitable for specific conditions is well within the knowledge of those skilled in the art of electroplating, there being a wide variety available from purveyors of nickel plating process.
  • Mild agitation of the bath, or relative movement between bath and cathode such as obtained by cathode movement or bath circulation is advantageous in maintaining uniform bath composition and therefore uniform deposit composition.
  • the passage of continuous steel strip through the plating bath while it is being plated is entirely adequate and bath circulation through a pump and filter is desirable to maintain the bath clean as well as in motion.
  • the method of plating steel strip with a zinc-nickel alloy which comprises: causing the strip to traverse an aqueous plating bath having a pH of from 2.5 to 3.5, in which nickel chloride and zinc chloride have been dissolved in sufiicient amounts for each gallon of the bath to have a zinc content of from 8 to 10 ounces and a nickel content of from 4 to 5 ounces; making said strip a cathode as it passes through said bath and maintaining an electroplating current density of from to amperes per square foot of cathode surface of the strip, whereby a zincnickel alloy coating is electrodeposited on the steel strip, said zinc-nickel alloy consisting of from 6.5 to 9.5% nickel with the remainder zinc, said coating having an expansive internal stress of about 500-1400 psi. and which coating also has substantially greater corrosion resistance than zinc.

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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 And Plating Baths Therefor (AREA)
US439268A 1965-03-12 1965-03-12 Electroplating a ductile zinc-nickel alloy onto strip steel Expired - Lifetime US3420754A (en)

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Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4216272A (en) * 1978-06-02 1980-08-05 Oxy Metal Industries Corporation Multiple zinc-containing coatings
DE3005159A1 (de) * 1979-02-15 1980-08-21 Sumitomo Metal Ind Verfahren zur plattierung von stahlbaendern mit einer zink-nickel-legierung
US4249999A (en) * 1979-03-30 1981-02-10 Sumitomo Metal Industries, Ltd. Electrolytic zinc-nickel alloy plating
NL8003962A (nl) * 1979-08-22 1981-02-24 Thomas Steel Strip Corp Werkwijze en inrichting voor het aanbrengen van deklagen van corrosiebestendige nikkel-zink-legeringen op staal, alsmede voortbrengselen die aldus bekleed zijn.
US4314893A (en) * 1978-06-02 1982-02-09 Hooker Chemicals & Plastics Corp. Production of multiple zinc-containing coatings
US4351713A (en) * 1979-08-22 1982-09-28 Thomas Steel Strip Corp. Electro-co-deposition of corrosion resistant nickel/zinc alloys onto steel substrates
DE3231054A1 (de) * 1981-08-21 1983-03-03 Ebara-Udylite Co. Ltd., Tokyo Waessriges elektrolytbad zur kathodischen abscheidung von zink-nickel-legierungen und seine verwendung
US4388160A (en) * 1980-02-20 1983-06-14 Rynne George B Zinc-nickel alloy electroplating process
GB2119814A (en) * 1982-05-10 1983-11-23 Cockerill Sambre Sa Process and plant for the continuous electrolytic deposit of a layer of zinc alloy with a high current density
EP0101793A2 (de) * 1982-07-24 1984-03-07 Hoesch Aktiengesellschaft Verfahren zur Herstellung von elektrolytisch legierverzinktem Stahlblech
US4491623A (en) * 1981-07-14 1985-01-01 Kabushiki Kaisha Kobe Seiko Sho Double-layer electroplated steel article with corrosion resistance after painting and wet adhesion of paint film
US4497876A (en) * 1983-03-16 1985-02-05 Kidon William E Corrosion resistant metal composite with zinc and chromium coating
US4500610A (en) * 1983-03-16 1985-02-19 Gunn Walter H Corrosion resistant substrate with metallic undercoat and chromium topcoat
US4524111A (en) * 1981-05-19 1985-06-18 Nippon Steel Corporation Weldable paint-coated steel sheets having excellent corrosion resistance
US4537837A (en) * 1983-03-16 1985-08-27 Gunn Walter H Corrosion resistant metal composite with metallic undercoat and chromium topcoat
DE3414048A1 (de) * 1984-04-13 1985-10-17 Nisshin Steel Co., Ltd., Tokio/Tokyo Verfahren zum herstellen von mit einer zink-nickel-legierung galvanisierten stahlteilen
US4569731A (en) * 1984-04-25 1986-02-11 Kawasaki Steel Corporation Production of Zn-Ni alloy plated steel strips
EP0248059A1 (en) * 1985-12-06 1987-12-09 Bethlehem Steel Corporation Ni-Zn ELECTROPLATED PRODUCT RESISTANT TO PAINT DELAMINATION
US4746408A (en) * 1987-11-05 1988-05-24 Whyco Chromium Company, Inc. Multi layer corrosion resistant coating
US4765871A (en) * 1981-12-28 1988-08-23 The Boeing Company Zinc-nickel electroplated article and method for producing the same
US4837090A (en) * 1987-11-05 1989-06-06 Whyco Chromium Company, Inc. Corrosion resistant coating for fasteners
US4975337A (en) * 1987-11-05 1990-12-04 Whyco Chromium Company, Inc. Multi-layer corrosion resistant coating for fasteners and method of making
US5275892A (en) * 1987-11-05 1994-01-04 Whyco Chromium Company, Inc. Multi-layer corrosion resistant coating for fasteners and method of making
EP0587933A1 (en) * 1992-09-15 1994-03-23 NIPPON MINING & METALS COMPANY, LIMITED Use of a Zn-Ni alloy for preparation of Zn-Ni alloy electroplating bath, use of a Zn-Ni alloy for preparation of Zn-Ni alloy hot-dip galvanizing plating bath, and method for producing a Zn-Ni alloy
EP0739995B1 (en) * 1992-09-16 1998-08-19 Nippon Mining & Metals Co., Ltd. Use of a Zn-Ni alloy for preparation of Zn-Ni alloy hot-dip galvanizing bath
US20090047540A1 (en) * 2005-03-07 2009-02-19 Material Sciences Corporation Colored acrylic coated metal substrate
US20140023879A1 (en) * 2011-03-29 2014-01-23 Fumio Shibao Surface-treated steel sheet and method of manufacturing the same
WO2018117751A1 (ko) 2016-12-23 2018-06-28 주식회사 포스코 내식성과 가공성이 우수한 zn-ni 전기도금강판 및 그 제조방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1928053A (en) * 1931-12-17 1933-09-26 American Brass Co Die cast zinc base alloy product
US2419231A (en) * 1940-12-21 1947-04-22 Standard Steel Spring Co Electroplated corrosion proof metal articles and method of making the same
FR940302A (fr) * 1946-02-07 1948-12-09 Standard Steel Spring Co Perfectionnements aux solutions pour le dépôt électrolytique du zinc et du nickel
US2989446A (en) * 1956-10-29 1961-06-20 Rockwell Standard Co Electroplating
US3064337A (en) * 1958-05-19 1962-11-20 Rockwell Standard Co Composite metal article

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1928053A (en) * 1931-12-17 1933-09-26 American Brass Co Die cast zinc base alloy product
US2419231A (en) * 1940-12-21 1947-04-22 Standard Steel Spring Co Electroplated corrosion proof metal articles and method of making the same
FR940302A (fr) * 1946-02-07 1948-12-09 Standard Steel Spring Co Perfectionnements aux solutions pour le dépôt électrolytique du zinc et du nickel
US2989446A (en) * 1956-10-29 1961-06-20 Rockwell Standard Co Electroplating
US3064337A (en) * 1958-05-19 1962-11-20 Rockwell Standard Co Composite metal article

Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4314893A (en) * 1978-06-02 1982-02-09 Hooker Chemicals & Plastics Corp. Production of multiple zinc-containing coatings
US4216272A (en) * 1978-06-02 1980-08-05 Oxy Metal Industries Corporation Multiple zinc-containing coatings
DE3005159A1 (de) * 1979-02-15 1980-08-21 Sumitomo Metal Ind Verfahren zur plattierung von stahlbaendern mit einer zink-nickel-legierung
FR2449140A1 (fr) * 1979-02-15 1980-09-12 Sumitomo Metal Ind Procede de placage d'une bande d'acier
US4249999A (en) * 1979-03-30 1981-02-10 Sumitomo Metal Industries, Ltd. Electrolytic zinc-nickel alloy plating
JPS5838517B2 (ja) * 1979-08-22 1983-08-23 ト−マス ステイ−ル ストリツプ コ−ポレ−シヨン 鉄または鋼の基体に耐食性保護被覆をメッキする方法
NL8003962A (nl) * 1979-08-22 1981-02-24 Thomas Steel Strip Corp Werkwijze en inrichting voor het aanbrengen van deklagen van corrosiebestendige nikkel-zink-legeringen op staal, alsmede voortbrengselen die aldus bekleed zijn.
JPS5633493A (en) * 1979-08-22 1981-04-03 Steel Strip Corp Thomas Cooelectrodeposition of corrosion resistant nickel zinc alloy to steel substrate
FR2468661A1 (fr) * 1979-08-22 1981-05-08 Thomas Steel Strip Corp Procede et appareil de placage electrolytique de revetement ni/zn projecteurs sur des supports metalliques
US4282073A (en) * 1979-08-22 1981-08-04 Thomas Steel Strip Corporation Electro-co-deposition of corrosion resistant nickel/zinc alloys onto steel substrates
US4351713A (en) * 1979-08-22 1982-09-28 Thomas Steel Strip Corp. Electro-co-deposition of corrosion resistant nickel/zinc alloys onto steel substrates
US4388160A (en) * 1980-02-20 1983-06-14 Rynne George B Zinc-nickel alloy electroplating process
US4524111A (en) * 1981-05-19 1985-06-18 Nippon Steel Corporation Weldable paint-coated steel sheets having excellent corrosion resistance
US4491623A (en) * 1981-07-14 1985-01-01 Kabushiki Kaisha Kobe Seiko Sho Double-layer electroplated steel article with corrosion resistance after painting and wet adhesion of paint film
DE3231054C2 (pt) * 1981-08-21 1989-04-27 Ebara-Udylite Co. Ltd., Tokio/Tokyo, Jp
DE3231054A1 (de) * 1981-08-21 1983-03-03 Ebara-Udylite Co. Ltd., Tokyo Waessriges elektrolytbad zur kathodischen abscheidung von zink-nickel-legierungen und seine verwendung
US4765871A (en) * 1981-12-28 1988-08-23 The Boeing Company Zinc-nickel electroplated article and method for producing the same
GB2119814A (en) * 1982-05-10 1983-11-23 Cockerill Sambre Sa Process and plant for the continuous electrolytic deposit of a layer of zinc alloy with a high current density
EP0101793A3 (de) * 1982-07-24 1986-06-04 Hoesch Aktiengesellschaft Verfahren zur Herstellung von elektrolytisch legierverzinktem Stahlblech
EP0101793A2 (de) * 1982-07-24 1984-03-07 Hoesch Aktiengesellschaft Verfahren zur Herstellung von elektrolytisch legierverzinktem Stahlblech
US4497876A (en) * 1983-03-16 1985-02-05 Kidon William E Corrosion resistant metal composite with zinc and chromium coating
US4537837A (en) * 1983-03-16 1985-08-27 Gunn Walter H Corrosion resistant metal composite with metallic undercoat and chromium topcoat
US4500610A (en) * 1983-03-16 1985-02-19 Gunn Walter H Corrosion resistant substrate with metallic undercoat and chromium topcoat
DE3414048A1 (de) * 1984-04-13 1985-10-17 Nisshin Steel Co., Ltd., Tokio/Tokyo Verfahren zum herstellen von mit einer zink-nickel-legierung galvanisierten stahlteilen
US4569731A (en) * 1984-04-25 1986-02-11 Kawasaki Steel Corporation Production of Zn-Ni alloy plated steel strips
EP0248059A1 (en) * 1985-12-06 1987-12-09 Bethlehem Steel Corporation Ni-Zn ELECTROPLATED PRODUCT RESISTANT TO PAINT DELAMINATION
EP0248059A4 (en) * 1985-12-06 1988-01-28 Bethlehem Steel Corp GALVANIZED PRODUCT WITH Ni-Zn RESISTANT TO PAINTING OF PAINT.
US4746408A (en) * 1987-11-05 1988-05-24 Whyco Chromium Company, Inc. Multi layer corrosion resistant coating
US4837090A (en) * 1987-11-05 1989-06-06 Whyco Chromium Company, Inc. Corrosion resistant coating for fasteners
US4975337A (en) * 1987-11-05 1990-12-04 Whyco Chromium Company, Inc. Multi-layer corrosion resistant coating for fasteners and method of making
US5275892A (en) * 1987-11-05 1994-01-04 Whyco Chromium Company, Inc. Multi-layer corrosion resistant coating for fasteners and method of making
EP0587933A1 (en) * 1992-09-15 1994-03-23 NIPPON MINING & METALS COMPANY, LIMITED Use of a Zn-Ni alloy for preparation of Zn-Ni alloy electroplating bath, use of a Zn-Ni alloy for preparation of Zn-Ni alloy hot-dip galvanizing plating bath, and method for producing a Zn-Ni alloy
EP0739995B1 (en) * 1992-09-16 1998-08-19 Nippon Mining & Metals Co., Ltd. Use of a Zn-Ni alloy for preparation of Zn-Ni alloy hot-dip galvanizing bath
US20090047540A1 (en) * 2005-03-07 2009-02-19 Material Sciences Corporation Colored acrylic coated metal substrate
US20140023879A1 (en) * 2011-03-29 2014-01-23 Fumio Shibao Surface-treated steel sheet and method of manufacturing the same
US9428823B2 (en) * 2011-03-29 2016-08-30 Nippon Steel & Sumitomo Metal Corporation Surface-treated steel sheet and method of manufacturing the same
WO2018117751A1 (ko) 2016-12-23 2018-06-28 주식회사 포스코 내식성과 가공성이 우수한 zn-ni 전기도금강판 및 그 제조방법
KR20180074149A (ko) 2016-12-23 2018-07-03 주식회사 포스코 내식성과 가공성이 우수한 Zn-Ni 전기도금강판 및 그 제조방법
EP3561156A4 (en) * 2016-12-23 2020-01-22 Posco ZN-NI GALVANOPLACED STEEL SHEET HAVING EXCELLENT CORROSION RESISTANCE AND SHAPING CHARACTERISTICS AND MANUFACTURING METHOD THEREOF

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