EP0121817A1 - Procédé pour fabriquer des toiles d'acier sans étain présentant une adhésion pour vernis - Google Patents

Procédé pour fabriquer des toiles d'acier sans étain présentant une adhésion pour vernis Download PDF

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Publication number
EP0121817A1
EP0121817A1 EP84102797A EP84102797A EP0121817A1 EP 0121817 A1 EP0121817 A1 EP 0121817A1 EP 84102797 A EP84102797 A EP 84102797A EP 84102797 A EP84102797 A EP 84102797A EP 0121817 A1 EP0121817 A1 EP 0121817A1
Authority
EP
European Patent Office
Prior art keywords
chromium
steel sheet
electrolytic chromate
aqueous solution
chromate treatment
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.)
Withdrawn
Application number
EP84102797A
Other languages
German (de)
English (en)
Inventor
Hajime C/O Research Laboratories Ogata
Kyoko C/O Research Laboratories Yamaji
Shunichi c/o Research Laboratories Tsugawa
Toshio C/O Research Laboratories Ichida
Toshio C/O Research Laboratories Irie
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.)
JFE Steel Corp
Original Assignee
Kawasaki Steel Corp
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 Kawasaki Steel Corp filed Critical Kawasaki Steel Corp
Publication of EP0121817A1 publication Critical patent/EP0121817A1/fr
Withdrawn legal-status Critical Current

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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
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/38—Chromatising
    • 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

Definitions

  • This invention relates to a method for producing tin-free steel sheets having improved lacquer adhesion.
  • Electrolytic chromate treated steel sheets also known as tin-free steel (TFS) of chromium type have improved properties as can-forming material and are regarded as a substitute for tin plates, and the demand for them is increasing in recent years.
  • TFS tin-free steel
  • a can is fabricated from a TFS sheet by coating a blank with an epoxy-phenol lacquer and cementing the mating edges of the coated blank with a polyamide adhesive to form a can barrel.
  • TFS cans are not only used for low-temperature packs prepared by packing contents such as carbonated beverage and beer in cans at relatively low temperatures, but also used for the so-called hot packs prepared by packing contents such as fruit juice in cans at relatively high temperatures for sterilization.
  • TFS is also used in those cans requiring a high temperature retorting treatment for sterilization at the end of packing of coffee, for example. In the latter applications, there often occurred accidents of rupture of can barrels.
  • This can barrel rupture occurs in cemented TFS cans during hot packing and retorting treatment because hot water penetrates through the coating at the barrel junction to deteriorate the interfacial adhesion between the lacquer coating and the TFS substrate to eventually separate the lacquer coating from the TFS.
  • the reverse electrolysis may be carried out in the chromium plating solution or in another aqueous solution containing chromium ion, with similar results with respect to lacquer adhesion.
  • the method characterized by inserting the reverse electrolysis step between the chromium plating and electrolytic chromate treatment steps is fully effective in improving lacquer adhesion.
  • the reversely electrolyzed steel sheet tends to suppress the growth of a chromium oxide layer thereon during the subsequent electrolytic chromate treatment, as long as the chromate bath contains at least one selected from chromic acid anhydride, chromates and dichromates and concomitant anions such as sulfate (SO 2- 4 ), fluoride (F - ) and chloride (Cl-) ions.
  • SO 2- 4 sulfate
  • F - fluoride
  • Cl- chloride
  • the surface state of steel sheets after chromium plating and reverse electrolysis was examined by the electron spectroscopy for chemical analysis (ESCA) or X-ray electron spectroscopy to find that as compared with the surface state observed after chromium plating, the quantity of anions codeposited in the chromium oxide layer is reduced and the bond energy of O 1S is shifted to a lower energy level, that is, from 531.4 eV to 530.1 eV as diagramatically shown in Fig. 1. This indicates that the proportion of ol linkages (Cr-OH) in the chromium oxide layer is reduced and the proportion of oxo linkages (Cr-O) is increased. This is the reason why the growth of a chromium oxide layer is suppressed on reversely electrolyzed steel sheets.
  • ESA electron spectroscopy for chemical analysis
  • X-ray electron spectroscopy X-ray electron spectroscopy
  • electrolytic chromate treatment was carried out in a variety of aqueous chromate solutions which contained at least one chromium compound selected from chromic acid anhydride,'chromates and dichromates as a main agent and at least one fluoride selected from H 2 SiF 6 , HBF 4 , HF and salts thereof and KAlF 4 as an additive.
  • aqueous chromate solutions which contained at least one chromium compound selected from chromic acid anhydride,'chromates and dichromates as a main agent and at least one fluoride selected from H 2 SiF 6 , HBF 4 , HF and salts thereof and KAlF 4 as an additive.
  • efficient electrolytic chromate treatment is carried out by carefully controlling the proportion of the chromium compound and the fluoride to a specific range.
  • an object of the present invention to provide an electrolytic chromate solution which allows chromium oxides to be effectively deposited on reversely electrolyzed steel sheets without detracting from subsequent lacquer adhesion.
  • Tin-free steel sheets are advantageously produced by the steps of chromium plating a thin steel sheet through cathodic electrolysis in a chromium ion-containing aqueous solution to form a layer consisting essentially of metallic chromium, reversely electrolyzing the chromium plated steel sheet by a successive anodizing treatment in said aqueous solution or in another chromium ion-containing aqueous solution, and subjecting the reversely electrolyzed steel sheet to an electrolytic chromate treatment in an aqueous solution of at least one selected from the group consisting of chromic acid, chromates, and dichromates.
  • the electrolytic chromate treatment should be carried out in the solution which contains hexavalent chromium in an amount of 0.2 to 1.4 mols of Cro 3 per liter of the solution and a fluoride in an amount to give a molar ratio of F - to Cr 6+ in the range of 1/1000 to 1/20.
  • the present invention is directed to TFS sheets having a layer of metallic chromium ranging from 50 to 200 mg per square meter on each sheet surface and a layer of hydrated chromium oxides ranging from 8 to 30 mg of Cr per square meter on the metallic chromium layer.
  • TFS sheets generally have a metallic chromium layer of 50 to 200 mg/m 2 because thinner layers of less than 50 mg/m 2 have poor corrosion resistance. Thicker layers exceeding 200 mg/m 2 do not provide an additional improvement in corrosion resistance.
  • TFS sheets have a layer of hydrated chromium oxides of 8 to 30 mg/m 2 (calculated as metallic chromium) because thinner layers of less than 8 mg/m 2 do not provide the necessary lacquer adhesion. Thicker layers exceeding 30 mg/m 2 have a poor appearance and are prone to cracking during subsequent processing and thus impractical.
  • the chromate solution in which the electrolytic chromate treatment was carried out contains as a main agent at least one chromium compound selected from chromic acid anhydride, chromates and dichromates.
  • concentration of the chromium compound should be limited to the range of 0.2 to 1.4 mols of CrO 3 per liter of the solution. At chromate concentrations of less than 0.2 mol/1, the growth of a chromium oxide layer is suppressed, failing to achieve the object of the invention. Chromate concentrations beyond 1.4 mol/l do not further increase the rate of formation of chromium oxides and are thus costly.
  • the additive which is intentionally added to the chromate solution is at least one fluoride which may be selected from H 2 SiF 6 , HBF 4 , HF and salts thereof, and KAIF 4 .
  • the following experiment was carried out to determine the optimum range of the fluoride ion (F ) concentration in the chromate solution.
  • the molar ratio of fluoride ion to hexavalent chromium ion (F - /Cr 6+ ) was varied over the range between 1/5000 and 1/5.
  • the electrolytic conditions for cathodic treatment were fixed to a current density of 15 A/dm 2 (amperes per square decimeter) and a time of 1 second. A number of reversely electrolyzed steel pieces were electrolytically chromated under these conditions. The amount of hydrated chromium oxides formed thereon was determined and lacquer adhesion was tested.
  • the concentration of the fluoride should be kept at a relatively lower level, that is, a molar ratio of F - /Cr 6+ in the range of 1/1000 to 1/20.
  • industrial grade chromate (Cr0 3 ) reagent contains a concomitant fluoride impurity in an amount to give a molar ratio of F - /Cr 6+ of the order of 1/5000.
  • the fluoride In order that the fluoride be sufficiently effective to promote the formation of chromium oxides, it must be present in an amount to give a molar ratio of F - /Cr 6+ of at least 1/1000 as seen from Fig. 2.
  • the lacquer adhesion was evaluated in the following manner by preparing a test sample as shown in Fig. 4.
  • a phenol-epoxy lacquer was applied to one surface of a treated steel sheet 1 to a build-up of 50 mg/dm' and baked for 10 minutes at 200°C to form a lacquer film 1A.
  • the same lacquer was applied to the opposite surface of the sheet 1 to a build-up of 50 mg/dm 2 and baked for 10 minutes at 200°C to form another lacquer film 1B.
  • the double-coated sheet was cut into pieces of 70 mm wide by 60 mm long. The longitudinal ends of two pieces were overlapped each other over a distance of 8 mm with a nylon film of 100 um thick interposed therebetween as shown in Fig. 4a.
  • the steel sheets were subjected to reverse electrolysis at a current density of 5 A/dm 2 for 0.2 seconds or at a current density of 10 A/dm 2 for 0.2 seconds while the sheet was made the anode in the same bath as used for chromium plating. For comparison sake, some steel sheets were not subjected to reverse electrolysis.
  • Cathodic treatment was carried out with an electricity quantity of 15 to 20 coulomb/dm 2 using different chromate baths based on CrO 3 and containing a variety of fluorides at a temperature of 40°C.
  • TFS sheets By carrying out (1) chromium plating, (2) reverse electrolysis, and (3) electrolytic chromate treatment in succession, there were prepared TFS sheets.
  • the amount of chromium oxides formed on the TFS sheets was determined by X-ray fluorometry and a retorting test was carried out to evaluate lacquer adhesion in the same manner as described previously. The results are shown in Table 1.

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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)
  • Electrochemical Coating By Surface Reaction (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Chemical Treatment Of Metals (AREA)
EP84102797A 1983-03-15 1984-03-14 Procédé pour fabriquer des toiles d'acier sans étain présentant une adhésion pour vernis Withdrawn EP0121817A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP4294283A JPS59170298A (ja) 1983-03-15 1983-03-15 塗料密着性にすぐれたテインフリ−鋼板の製造方法
JP42942/83 1983-03-15

Publications (1)

Publication Number Publication Date
EP0121817A1 true EP0121817A1 (fr) 1984-10-17

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EP84102797A Withdrawn EP0121817A1 (fr) 1983-03-15 1984-03-14 Procédé pour fabriquer des toiles d'acier sans étain présentant une adhésion pour vernis

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EP (1) EP0121817A1 (fr)
JP (1) JPS59170298A (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0184115A1 (fr) * 1984-11-29 1986-06-11 Kawasaki Steel Corporation Ruban d'acier à surface traitée ayant une soudabilité améliorée et procédé de fabrication
EP0194654A1 (fr) * 1985-03-15 1986-09-17 Kawasaki Steel Corporation Rubans d'acier sans étain utilisables pour la fabrication de boîtes soudées et procédé de production
EP0250792A1 (fr) * 1986-05-12 1988-01-07 Nippon Steel Corporation Traitement au chromate d'une tôle d'acier revêtue de métal
EP0101871B1 (fr) * 1982-07-20 1988-09-28 Kawasaki Steel Corporation Procédé de fabrication de tôles d'acier exemptes d'étain présentant une résistance améliorée pendant le traitement de pliage
GB2209177A (en) * 1987-08-27 1989-05-04 Nippon Sheet Glass Co Ltd Method for production of oxide film by treating substrates with supersaturated metal oxide solution
CN108368615A (zh) * 2015-12-11 2018-08-03 杰富意钢铁株式会社 罐用钢板及其制造方法
WO2021148318A1 (fr) * 2020-01-23 2021-07-29 Mahle International Gmbh Composition servant d'électrolyte pour dissoudre et/ou séparer des métaux, des oxydes métalliques et/ou des alliages métalliques et utilisations de cette composition

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1436150A (en) * 1970-05-26 1976-05-19 Int Nickel Ltd Electrolytic treatment of chromium containing alloys and electrolytes for use therein
EP0101871A1 (fr) * 1982-07-20 1984-03-07 Kawasaki Steel Corporation Procédé de fabrication de tôles d'acier exemptes d'étain présentant une résistance améliorée pendant le traitement de pliage

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6040519B2 (ja) * 1981-04-25 1985-09-11 川崎製鉄株式会社 テインフリ−鋼板の製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1436150A (en) * 1970-05-26 1976-05-19 Int Nickel Ltd Electrolytic treatment of chromium containing alloys and electrolytes for use therein
EP0101871A1 (fr) * 1982-07-20 1984-03-07 Kawasaki Steel Corporation Procédé de fabrication de tôles d'acier exemptes d'étain présentant une résistance améliorée pendant le traitement de pliage

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 97, no. 12, September 1982, page 569, no. 100694a, Columbus, Ohio, USA; & JP - A - 82 57893 (NIPPON STEEL CORP.) 07-04-1982 *
CHEMICAL ABSTRACTS, vol. 98, no. 12, March 1983, page 531, no. 97966d, Columbus, Ohio, USA; & JP - A - 57 45479 (KAWASAKI STEEL CORP.) 28-09-1982 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0101871B1 (fr) * 1982-07-20 1988-09-28 Kawasaki Steel Corporation Procédé de fabrication de tôles d'acier exemptes d'étain présentant une résistance améliorée pendant le traitement de pliage
EP0184115A1 (fr) * 1984-11-29 1986-06-11 Kawasaki Steel Corporation Ruban d'acier à surface traitée ayant une soudabilité améliorée et procédé de fabrication
EP0194654A1 (fr) * 1985-03-15 1986-09-17 Kawasaki Steel Corporation Rubans d'acier sans étain utilisables pour la fabrication de boîtes soudées et procédé de production
US4687713A (en) * 1985-03-15 1987-08-18 Kawasaki Steel Corporation Tin-free steel strips useful in the manufacture of welded cans and process for making
EP0250792A1 (fr) * 1986-05-12 1988-01-07 Nippon Steel Corporation Traitement au chromate d'une tôle d'acier revêtue de métal
GB2209177A (en) * 1987-08-27 1989-05-04 Nippon Sheet Glass Co Ltd Method for production of oxide film by treating substrates with supersaturated metal oxide solution
US4882183A (en) * 1987-08-27 1989-11-21 Nippon Sheet Glass Co., Ltd. Method for production of oxide film
GB2209177B (en) * 1987-08-27 1992-01-15 Nippon Sheet Glass Co Ltd Method for production of oxide film
CN108368615A (zh) * 2015-12-11 2018-08-03 杰富意钢铁株式会社 罐用钢板及其制造方法
EP3388549A4 (fr) * 2015-12-11 2018-10-31 JFE Steel Corporation Tôle d'acier pour canettes et procédé de fabrication de tôle d'acier pour canettes
US10753005B2 (en) 2015-12-11 2020-08-25 Jfe Steel Corporation Steel sheet for cans and production method for steel sheet for cans
WO2021148318A1 (fr) * 2020-01-23 2021-07-29 Mahle International Gmbh Composition servant d'électrolyte pour dissoudre et/ou séparer des métaux, des oxydes métalliques et/ou des alliages métalliques et utilisations de cette composition

Also Published As

Publication number Publication date
JPS59170298A (ja) 1984-09-26

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Inventor name: IRIE, TOSHIOC/O RESEARCH LABORATORIES

Inventor name: TSUGAWA, SHUNICHIC/O RESEARCH LABORATORIES

Inventor name: OGATA, HAJIMEC/O RESEARCH LABORATORIES

Inventor name: ICHIDA, TOSHIOC/O RESEARCH LABORATORIES

Inventor name: YAMAJI, KYOKOC/O RESEARCH LABORATORIES