US3316160A - Process for electrolytic chromium-plating steel strips without a bluish tint while using two or more plating tanks - Google Patents

Process for electrolytic chromium-plating steel strips without a bluish tint while using two or more plating tanks Download PDF

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Publication number
US3316160A
US3316160A US300589A US30058963A US3316160A US 3316160 A US3316160 A US 3316160A US 300589 A US300589 A US 300589A US 30058963 A US30058963 A US 30058963A US 3316160 A US3316160 A US 3316160A
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United States
Prior art keywords
plating
tank
path
steel strip
wire
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Expired - Lifetime
Application number
US300589A
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English (en)
Inventor
Uchida Hiromu
Yanabu Osamu
Hada Takashi
Adachi Takeo
Jun Tsujimoto
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Fuji Iron and Steel Co Ltd
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Fuji Iron and Steel Co Ltd
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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
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • 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
    • Y10S205/00—Electrolysis: processes, compositions used therein, and methods of preparing the compositions
    • Y10S205/917—Treatment of workpiece between coating steps
    • 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
    • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
    • Y10T428/12826—Group VIB metal-base component
    • Y10T428/12847—Cr-base component
    • Y10T428/12854—Next to Co-, Fe-, or Ni-base component

Definitions

  • This invention relates to a process for producing electrolytic chromium-plated steel strips using more than two plating paths or plating tanks and, more particularly, to an economical and advantageous process of this type in Which the electrolytic chromium-plated steel strip is produced without a bluish tint.
  • the invention process has been developed and by this process chromium-plated steel strips without a bluish tint may be easily and advantageously obtained even when there are two or more plating tanks, or two or more plating paths in a single tank.
  • the essence of the present invention resides in using certain specific treatment conditions within successive tanks or paths as cept the first tank or path.
  • electrolytically chromium-plated steel without the bluish tint, is provided by moving the steel strip through more than two tanks or paths, and in each of the plating tanks or paths after the first, imparting to the steel strip a cathodic treatment under low current density succeeded by chromium plating in the same path or tank.
  • the present invention may rely upon the known Surgeant bath for the chromium plating process.
  • the cathodic treatment is effected by maintaining the steel strip negative with a current density of about 0.1-l0 a./dm. for 0.01 to 3 seconds.
  • the eificiency of removing the said bluish tint will be insufiicient if the current density is greater than about a./dm. or less than 0.1 a./dm.
  • an electrolytic chromiumplated steel without the bluish tint may be obtained even if there are two or more plating tanks used or two or more plating paths, and the steel strip obtained will have a 2 lustrous silvery white color such as is obtained by using only one plating tank or path.
  • the present invention is applicable to plating using vertical type or tanks of a horizontal
  • plating is effected in each tank during the downward path of the strip or wire and, after the latter passes over the sink roll, in the upwith low current density before the plating.
  • An electrolytically chromium-plated steel strip without a bluish tint may thus be obtained advantageously by using more than two plating tanks.
  • the steel strip or wire may be provided with a preliminary plating of a thin layer of. copper, nickel or alloys thereof.
  • the present invention is based upon the discovery that plating tank,
  • a feature of the invention plating tanks, in each tank after the first the downward manner as mentioned above.
  • the material used for the shielding plate or plates must be dielectric and corrosion resistant, such as, for example, vinyl chloride or the like.
  • FIG. 1 is a somewhat schematic and diagrammatic side elevational view illustrating the practice of the present invention using vertical plating tanks;
  • FIG. '2 is a somewhat schematic and diagrammatic side elevation illustrating the practice of the invention using horizontal plating tanks
  • FIG. 3a is a partial elevational view illustrating one of the shielding plates or members in association with the strip to be treated;
  • FIG. 3b is a sectional view taken on the line AA of FIG. 3a.
  • FIG. 3c is a sectional view taken FIG. 3a.
  • the steel strip or wire is led from an uncoiler roll 1 through pinch rolls 2, a welder 3, and a driving and tensioning roll assembly 4, the strip being led into an electrolytic degreasing tank 5.
  • the strip is led through a water tank 6, where the strip is washed, an electrolytic pickling tank 7 and a waterwashing tank 8 where the strip is again washed.
  • the strip is then led into the first plating tank 9.
  • electrolytic chromium plating is effected in a downward path 10 and an upward path 11.
  • the steel strip is then led into a second plating tank 12 which is provided with the aforementioned shielding means A positioned so as to cover the upper portion of the downward path 13.
  • the strip is given a cathodic treatment which is effected by the relatively small electric current flowing through the small holes in the shielding plate.
  • the strip is electrolytically chromium-plated in the upward path 14.
  • the treatment given to the strip in tank 12 is repeated in each of the tanks '15, 16 and .17, utilizing shielding plates or casings B, C and D corresponding to the plate or casing A.
  • the steel strip or wire emerging from the tank 17 is then passed through a washing tank 18, a chemical treating tank 19, and a hot Water washing tank 20.
  • the strip is then sprayed with oil in an emulsion-oiling tank 21 and coated with a predetermined amount of oil film by means of the squeezing rolls 22.
  • the steel strip is then dried in drying furnace 23 and coiled on a coiling roll 25 after passing through tensioning and driving roll assembly 24.
  • components 26 and 27 are D.C. sources for the electrolytic degreasing and electrolytic pickling.
  • D.C. sources 28 through 32 are used for each of the plating tanks 9, 12, 1'5, 1 6 and 17, respectively.
  • FIG. 2 illustrates the invention as used with horizontal plating tanks.
  • the steel strip or wire is led from the uncoiler means 33 into an electrolytic degreasing tank 37 after passing through pinch rolls 34, welder and a tension and driving roll assembly 36.
  • the strip is passed through a brush scrubber 38, an electrolytic pickling tank 39, a brush scrubber 40, and over an electric potential applying conductor roll 41 into the first plating tank 43.
  • Roll 41 is connected to the negative terminal of D.C. source 66.
  • electrolytic plating is effected by means of an electrode 42, connected to the positive terminal of source 66.
  • the strip of wire is then led into the second plating tank 46 over a conductor roll 44 connected to the negative terminal of source 67.
  • cathodic treatment using a very small current is effected at the entrance portion to the electrode 45 by means of a shielding plate A which may be the same as previously described.
  • the strip is electrolytically plated in the usual manner.
  • Electrode 45 is connected to the positive terminal of D.C. source 67.
  • each of the succeeding plating tanks 49 to 52 and 55 cathodic treatments followed by electroplating are effected in the same manner as mentioned for tanks 46.
  • the strip or wire passes over a conductor roll 47, 50 or 53, respectively, connected to the negative terminal of a D.C. source 68, 69 and 70, respectively.
  • Electrodes 48, 51 and 54 are provided in the respective tanks 49, 52 and 55, and are connected to the respective positive terminals of the sources 68, 69 and 70.
  • the shielding dielectric and corrosion resistant plates B, C and D are positioned to enclose the strip as the strip enters the electrodes 48, 51 and 54, respectively.
  • the strip of wire passes over the on the line B-B of roll 56, which is connected to the negative terminal of the D.C. source 66, and then into a washing tank 57 after which the strip passes through a chemical treating tank 58 and a hot water washing tank 59 before it is sprayed with oil in the emulsion oiling tank 60 and coated with a predetermined thickness of oil film by means of pressure roll 52.
  • the steel strip is then dried in the drying furnace 63 and coiled on a recoiler 65 after passing through the driving and tensioning roll assembly 64.
  • the D.C. current sources for the degreasing tank 37 and the pickling tank 39 are illustrated at 71 and 72.
  • each shielding plate A which is also representative of the shielding plates B, C and D, is a fiat rectangle in cross-section and has a substantial lateral and longitudinal extent with respect to the strip S.
  • One wide surface or wall of each plate or casing A is imperforate, while the opposite parallel surface is formed with the very small perforations 73. These very small perforations greatly decrease the current flow to the strip S, while the latter is passing through the shielding plate A.
  • Example I A steel strip having 0.25 mm. thickness is electrolytically degreased at 30 C. in a degreasing solution containing 5% caustic soda and 3% sodium silicate, with a current density of 40 a./dm. for two seconds. It is then washed by water and is electrolytically pickled in a 5% solution of sulfuric acid with a current density of 20 a./dm. for two seconds. It is washed with water again, and while keeping the temperature of the chromium plating electrolyte, which contains 250 g./l. of chromic acid anhydride and 2.5 g./l.
  • the strip is then subjected to cathodic treatment in the downward path of the second plating tank (the vertical type) with a current density of 3 a./dm. for 0.5 second, and to plating in the upward path with a current density of 30 a./dm. for one second.
  • the plating is effected in the same manner as in the second plating tank. Chromium coating of 0.05 micron thickness, having a lustrous silver white color, is thus made on the steel strip.
  • the steel strip is then washed by water and dipped in a 1% chromic acid water solution at 50 C. for two seconds and after being washed by hot water, it is oiled by an emulsion-Oiler and is coiled on the recoiler.
  • Example 11 A steel strip having 0.25 mm. thickness, which has been subjected to electrolytic degreasing and electrolytic picking in the same manner as Example I, is plated in the first plating tank (vertical type) with a current density of 40 a./dm. for one second in each of the downward path and the upward path, while keeping the temperature of the chromium plating electrolyte, containing 200 g./l. of chromic acid anhydride and 2 g./l. of sulfuric acid, at 50 C. The strip is then subjected to cathodic treatment in the downward path of the second plating tank, with a current density of 5 a./dm. for 0.2 second, and then plated, with a current density of 40 a./dm. for one second, in the upward path.
  • the plating is effected in the same manner as in the second plating tank, and thus chromium coating of about 0.06 micron thickness, having a lustrous silver white color, is obtained on the steel strip.
  • Example 111 A steel strip having 0.25 mm. thickness, which has been subjected to electrolytic degreasing and electrolytic pickling in the same manner as Example I, is plated in the first plating tank (vertical type) with a current density of 30 a./dm. for one second, in both the downward path and the upward path, while keeping the temperature of the chromium plating electrolyte, which contains 200 g./l. of chromic acid anhydride and 2.0 g./l. of sulfuric acid, at 50 C.
  • the strip is then subjected to cathodic treatment in the downward path of the second plating tank with a low current density of about 5 a./dm. restricted by means of the shielding plate, for about 0.1 second and then plated, with a current density of about 30 a./dm. for about 0.9 second.
  • the plating is effected, without any shielding plate, at a current density of 30 a./dm. for about one second.
  • the plating acid at 50 C. It is then subjected to cathodic treatment in the second plating tank (the horizontal type) with a low current density of about 1 a./dm. by passing through a shielding plate having small holes, on the inlet side of the electrode, for about 0.3 second, and then plated with a current density of 30 a./dm. after leaving the shielding plate, for about 1.2 seconds.
  • cathodic treatment is effected by using shielding plates on the inlet side of the electrode.
  • Plating is then effected in the same manner as in the second plating tank, and thus chromium coating of 0.05 micron thickness, having a lustrous silver white color, is obtained on the steel strip.
  • a process for obtaining an electrolytic chromiumplated steel strip or Wire having a lustrous chrorninum coating, characterized by the absence of a bluish tint comprising the steps of passing the steel strip or wire through more than two plating paths; in the second path and in each succeeding path the second path, initially at a low current density of 0.1 to a/dm. thereafter, in each plating path, chromium-plating the steel strip or Wire; and intermediate each plating path withdrawing the steel strip or wire from the plating solution.
  • a process for electrolytically chromium-plating steel strip or wire to obtain a lustrous coating characterized by the absence of a bluish tint comprising the steps of passing the steel strip or wire along more than two horizontal plating paths each having an activating electrode disposed therealong; in the second path and in each path succeeding the second path, in advance of the: steel strip orwire passing the activating electrode, passing the steel strip or wire through shielding means formed with a preselected number of very small apertures to reduce the currentflow to the strip or wire to a value which is only a minor fracplating action; in the activating electrode, a normal chromium plating current flow; and, intermediate each plating path, withdrawing the steel strip or wire from the solution.
  • a process for obtaining an electrolytically chromium-plated steel strip having a lustrous chromium coating characterized by the absence of a bluish tint, comprising or wire through more each tank succeeding the second tank, chromium-plating the steel strip or wire; and intermediate each plating path withdrawing the steel strip or wire from the plating solution.

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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)
US300589A 1962-08-16 1963-08-07 Process for electrolytic chromium-plating steel strips without a bluish tint while using two or more plating tanks Expired - Lifetime US3316160A (en)

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JP3547462 1962-08-16
JP5448062 1962-12-03

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3397133A (en) * 1960-03-21 1968-08-13 Benjamin B Doch Apparatus for producing silver nitrate
US3498892A (en) * 1966-05-04 1970-03-03 M & T Chemicals Inc Electrodeposition of chromium upon a continuous metal strip
US3532608A (en) * 1967-09-29 1970-10-06 United States Steel Corp Method of treating steel and electrolyte therefor
US3535213A (en) * 1967-12-20 1970-10-20 Yawata Seitetsu Kk Method of surface-treating metals
US3537971A (en) * 1967-08-07 1970-11-03 Rca Corp Apparatus for electroplating a ribbon
US3642587A (en) * 1970-07-06 1972-02-15 United States Steel Corp Chromium electroplating process and product thereof
US3755091A (en) * 1969-06-19 1973-08-28 Nat Steel Corp Process for reducing discoloration of electrochemically treated chromium plated ferrous metal strip
US4214961A (en) * 1979-03-01 1980-07-29 Swiss Aluminium Ltd. Method and apparatus for continuous electrochemical treatment of a metal web
US4624751A (en) * 1983-06-24 1986-11-25 American Cyanamid Company Process for fiber plating and apparatus with special tensioning mechanism
US4898649A (en) * 1988-02-27 1990-02-06 Nkk Corporation Method for manufacturing electrolytically chromated steel sheet
US4904351A (en) * 1982-03-16 1990-02-27 American Cyanamid Company Process for continuously plating fiber
US4911797A (en) * 1983-06-24 1990-03-27 American Cyanamid Company Contact roller mounting assembly and tensioning mechanism for electroplating fiber
WO2003095713A1 (en) * 2002-05-07 2003-11-20 University Of Southern California Conformable contact masking methods and apparatus utilizing in situ cathodic activation of a substrate
WO2018087135A1 (en) 2016-11-14 2018-05-17 Tata Steel Ijmuiden B.V. Method for electroplating an uncoated steel strip with a plating layer
EP3666928A1 (de) * 2018-12-13 2020-06-17 ThyssenKrupp Rasselstein GmbH Verfahren zur herstellung eines mit einer beschichtung aus chrom und chromoxid beschichteten metallbands auf basis einer elektrolytlösung mit einer dreiwertigen chromverbindung
US11274373B2 (en) 2018-12-13 2022-03-15 Thyssenkrupp Rasselstein Gmbh Method for the production of a metal strip coated with a coating of chromium and chromium oxide using an electrolyte solution with a trivalent chromium compound

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1794973A (en) * 1928-03-27 1931-03-03 Westinghouse Electric & Mfg Co Continuous method of chromium plating metallic wires or strips
US2266330A (en) * 1935-12-23 1941-12-16 John S Nachtman Process for electroplating strip steel
US2619454A (en) * 1945-08-30 1952-11-25 Brush Dev Co Method of manufacturing a magnetic recording medium by electrodeposition
GB727789A (en) * 1952-06-23 1955-04-06 Champion Paper & Fibre Co Improvements in electro-deposition of chromium

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1794973A (en) * 1928-03-27 1931-03-03 Westinghouse Electric & Mfg Co Continuous method of chromium plating metallic wires or strips
US2266330A (en) * 1935-12-23 1941-12-16 John S Nachtman Process for electroplating strip steel
US2619454A (en) * 1945-08-30 1952-11-25 Brush Dev Co Method of manufacturing a magnetic recording medium by electrodeposition
GB727789A (en) * 1952-06-23 1955-04-06 Champion Paper & Fibre Co Improvements in electro-deposition of chromium

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3397133A (en) * 1960-03-21 1968-08-13 Benjamin B Doch Apparatus for producing silver nitrate
US3498892A (en) * 1966-05-04 1970-03-03 M & T Chemicals Inc Electrodeposition of chromium upon a continuous metal strip
US3537971A (en) * 1967-08-07 1970-11-03 Rca Corp Apparatus for electroplating a ribbon
US3532608A (en) * 1967-09-29 1970-10-06 United States Steel Corp Method of treating steel and electrolyte therefor
US3535213A (en) * 1967-12-20 1970-10-20 Yawata Seitetsu Kk Method of surface-treating metals
US3755091A (en) * 1969-06-19 1973-08-28 Nat Steel Corp Process for reducing discoloration of electrochemically treated chromium plated ferrous metal strip
US3642587A (en) * 1970-07-06 1972-02-15 United States Steel Corp Chromium electroplating process and product thereof
US4214961A (en) * 1979-03-01 1980-07-29 Swiss Aluminium Ltd. Method and apparatus for continuous electrochemical treatment of a metal web
US4904351A (en) * 1982-03-16 1990-02-27 American Cyanamid Company Process for continuously plating fiber
US4624751A (en) * 1983-06-24 1986-11-25 American Cyanamid Company Process for fiber plating and apparatus with special tensioning mechanism
US4911797A (en) * 1983-06-24 1990-03-27 American Cyanamid Company Contact roller mounting assembly and tensioning mechanism for electroplating fiber
US4898649A (en) * 1988-02-27 1990-02-06 Nkk Corporation Method for manufacturing electrolytically chromated steel sheet
WO2003095713A1 (en) * 2002-05-07 2003-11-20 University Of Southern California Conformable contact masking methods and apparatus utilizing in situ cathodic activation of a substrate
US20070163888A1 (en) * 2002-05-07 2007-07-19 University Of Southern California Conformable Contact Masking Methods and Apparatus Utilizing In Situ Cathodic Activation of a Substrate
US20080210563A1 (en) * 2002-05-07 2008-09-04 University Of Southern California Conformable Contact Masking Methods and Apparatus Utilizing In Situ Cathodic Activation of a Substrate
WO2018087135A1 (en) 2016-11-14 2018-05-17 Tata Steel Ijmuiden B.V. Method for electroplating an uncoated steel strip with a plating layer
CN110062819A (zh) * 2016-11-14 2019-07-26 塔塔钢铁艾默伊登有限责任公司 用于使用镀覆层电镀未涂覆的钢带材的方法
RU2743357C2 (ru) * 2016-11-14 2021-02-17 Тата Стил Эймейден Б.В. Способ электроплакирования непокрытой стальной полосы плакирующим слоем
CN110062819B (zh) * 2016-11-14 2021-07-23 塔塔钢铁艾默伊登有限责任公司 用于使用镀覆层电镀未涂覆的钢带材的方法
EP3666928A1 (de) * 2018-12-13 2020-06-17 ThyssenKrupp Rasselstein GmbH Verfahren zur herstellung eines mit einer beschichtung aus chrom und chromoxid beschichteten metallbands auf basis einer elektrolytlösung mit einer dreiwertigen chromverbindung
CN111321432A (zh) * 2018-12-13 2020-06-23 蒂森克虏拉塞斯坦有限公司 用于制造涂覆有涂层的金属带的方法
KR20200074030A (ko) * 2018-12-13 2020-06-24 티센크루프 라셀쉬타인 게엠베하 3가 크롬 화합물이 함유된 전해질 용액을 사용하여 크롬 및 산화크롬 코팅으로 코팅된 금속 스트립의 제조방법
US11274373B2 (en) 2018-12-13 2022-03-15 Thyssenkrupp Rasselstein Gmbh Method for the production of a metal strip coated with a coating of chromium and chromium oxide using an electrolyte solution with a trivalent chromium compound
CN111321432B (zh) * 2018-12-13 2022-06-10 蒂森克虏拉塞斯坦有限公司 用于制造涂覆有涂层的金属带的方法
US11396713B2 (en) 2018-12-13 2022-07-26 Thyssenkrupp Rasselstein Gmbh Method for the production of a metal strip coated with a coating of chromium and chromium oxide using an electrolyte solution with a trivalent chromium compound

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GB991310A (en) 1965-05-05
BE635457A (zh)
DE1267052B (de) 1968-04-25

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