EP0352399B1 - Procédé de post-traitement chimique de surfaces de bandes en acier - Google Patents

Procédé de post-traitement chimique de surfaces de bandes en acier Download PDF

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Publication number
EP0352399B1
EP0352399B1 EP88890198A EP88890198A EP0352399B1 EP 0352399 B1 EP0352399 B1 EP 0352399B1 EP 88890198 A EP88890198 A EP 88890198A EP 88890198 A EP88890198 A EP 88890198A EP 0352399 B1 EP0352399 B1 EP 0352399B1
Authority
EP
European Patent Office
Prior art keywords
pickling liquid
acid
water
pickling
zinc
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
EP88890198A
Other languages
German (de)
English (en)
Other versions
EP0352399A1 (fr
Inventor
Kurt Dipl.-Ing. Dr. Kösters
Franz M. Dipl.-Ing. Androsch
Dieter Dipl.-Ing. Dr. Paesold
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.)
Voestalpine Stahl Linz GmbH
Original Assignee
Voestalpine Stahl Linz GmbH
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 Voestalpine Stahl Linz GmbH filed Critical Voestalpine Stahl Linz GmbH
Priority to DE8888890198T priority Critical patent/DE3871143D1/de
Priority to EP88890198A priority patent/EP0352399B1/fr
Priority to ES198888890198T priority patent/ES2033017T3/es
Priority to AT88890198T priority patent/ATE76115T1/de
Priority to US07/387,080 priority patent/US5043022A/en
Publication of EP0352399A1 publication Critical patent/EP0352399A1/fr
Application granted granted Critical
Publication of EP0352399B1 publication Critical patent/EP0352399B1/fr
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
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
    • C25D5/028—Electroplating of selected surface areas one side electroplating, e.g. substrate conveyed in a bath with inhibited background plating
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/088—Iron or steel solutions containing organic acids

Definitions

  • the invention relates to a method for the treatment of steel sheets electrolytically galvanized on one side, the non-galvanized side being brought into contact with an aqueous pickling liquid which contains an organic acid.
  • the coverings in question differ significantly from conventional rust, which forms, for example, on iron surfaces in the open air: While conventional rusting can be detached from the iron surface by heating in dilute hydrochloric acid with the formation of soluble iron (III) chloride, this is also possible not the coverings in question. In fact, they are so resistant that they cannot even be dissolved by hot, 10% hydrochloric acid. The reason for this unusual chemical behavior is likely to be iron-manganese spinels in the yellow or brown colors of the non-galvanized surface.
  • DE-A - 29 42 934 relates to a process for the detachment of surface oxide layers which arise during a thermal treatment of steel sheets by means of organic acids, with the pickling liquid being oxidized to Fe3+ by adding H2O2 Fe2+ and as such can be canceled.
  • DE-B-20 41 871 describes a process for pretreating steel sheets before phosphating them and then painting them with a de-solvent which contains more than 5% citric acid.
  • magnetite can be detached from metal surfaces with a pickling liquid containing an organic acid.
  • Neither of these methods is suitable for removing the particularly resistant oxide layer on the non-galvanized side of one-sided galvanized steel sheets.
  • the invention has for its object to eliminate this disadvantage and to provide a method for removing the coating on the non-galvanized side of galvanized steel sheets, which further ensures passivation of the metallic surface created with it, so that it does not subsequently lead to the formation of an iron hydroxide film can come, of course, the galvanized side must not be affected.
  • a pickling liquid is used in the method described above, which further contains a water-soluble peroxy compound, preferably hydrogen peroxide, and as organic acid only a water-soluble hydroxycarboxylic acid.
  • the present invention is based on the finding that the said coating can be removed very easily if the side of the steel sheet to be cleaned is treated with a pickling solution which contains a water-soluble hydroxycarboxylic acid and a water-soluble peroxo compound. If such a pickling solution is used, a mechanical cleaning step is unnecessary, which naturally has a positive effect on the surface quality of the steel sheet.
  • Particularly suitable are those hydroxycarboxylic acids which carry the hydroxyl group and the carboxyl group on one and the same carbon atom, such as malic acid or in particular citric acid, which has been found to be particularly suitable.
  • the pickling liquid used according to the invention is known per se from EP-A - 0 183 894; So far, however, it has only been used to remove iron and manganese deposits in drinking water supply systems.
  • the pickling liquid advantageously has a pH of 1.0 to 3.5, preferably 2 to 3.5, the hydroxycarboxylic acid in a concentration of 10 to 100 g / l and the peroxo compound in a concentration corresponding to 0.1 to 7 g of active oxygen / l are present.
  • An inorganic acid can also be added to adjust the pH of the pickling solution.
  • the pickling liquid used according to the invention can dissolve such a particularly resistant coating because the acidity of hydroxycarboxylic acids is far below that of hydrochloric acid and the reaction temperature is relatively low, preferably a maximum of 40 ° C.
  • the pickling liquid used according to the invention has both an acidic and a complexing and oxidizing effect.
  • the interaction of these three effects is attributed to the particular solubility and the passivating effect of the pickling liquid according to the invention.
  • the process according to the invention can be carried out very simply by continuously spraying the steel sheet through a pickling zone in which the non-galvanized side with pickling liquid and the galvanized side with water are homogeneously sprayed over the entire width of the steel sheet, and then through a washing zone which both sides are rinsed with water, which is then squeezed out, whereupon an extended water rinse is carried out if necessary.
  • the cross section of a chamber is shown schematically, in which the pickling and rinsing of the one-sided galvanized steel sheets is carried out.
  • the steel sheets are guided with the non-galvanized side upwards into a front pickling zone 4, in which they are sprayed with pickling liquid from above and with water from below.
  • the pickling liquid is fed into a line 5 a spray bar 6, which sprays the pickling liquid across the entire width of the steel sheet.
  • the sheet is sprayed from below with water, which is fed in line 7 to a plurality of spray bars 8, which likewise cover the entire width of the steel sheets.
  • the steel sheets After passing through the pickling zone 4, the steel sheets enter the washing zone 9, in which the pickling liquid is rinsed off with water, which is fed to the spray bar 11 by means of a line 10.
  • the reaction path which results from the distance between the two spray bars 6 and 11, is approximately 1 m. This short reaction path is sufficient to dissolve the oxide layer, the steel sheets being passed through the chamber at a speed of up to 90 m / min.
  • the sprayed-on water is removed by means of squeeze rollers 12 and, if desired, the pickled surface is sprayed again with water, which is fed to a spray bar 14 by means of a line 13. With 15 and 16 openings in the chamber are designated, at which washing liquid can be drained or drizzle can be suctioned off.
  • the non-galvanized side was found to be free from mixed oxides and discolouration after washing passivated with citric acid.
  • the galvanized side was not affected by the pickling.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Chemical Treatment Of Metals (AREA)

Claims (6)

1. Procédé de traitement de tôles d'acier galvanisées électrolytiquement sur une seule face, où la face non galvanisée est mise en contact avec un liquide de décapage aqueux, ce liquide de décapage contenant un acide organique, caractérisé en ce que l'on emploie un liquide de décapage qui contient également un composé peroxo hydrosoluble, de préférence du peroxyde d'hydrogène, et quine contient comme acide organique qu'un seul acide hydroxycarboxylique hydrosoluble.
2. Procédé selon la revendication 1, caractérisé en ce que l'on utilise un acide hydroxycarboxylique qui porte le groupement hydroxyle et le groupement carboxyle sur un seul et même atome de carbone.
3. Procédé selon la revendication 2, caractérisé en ce que l'on utilise comme acide hydroxycarboxylique de l'acide citrique.
4. Procédé selon une ou plusieurs des revendications 1 à 3, caractérisé en ce que le liquide de décapage présente un pH de 1,0 à 3,5, de préférence de 2 à 3,5, la concentration de l'acide hydroxycarboxylique étant de 10 à 100 g/l et celle du composé peroxo correspondant à 0,1 à 7 g d'oxygène actif/litre.
5. Procédé selon la revendication 4, caractérisé en ce que l'on ajoute au liquide de décapage, pour régler son pH, un acide anorganique.
6. Procédé selon la revendication 1, caractérisé en ce que la tôle d'acier (1) est envoyée en continu dans une zone de décapage (4) dans laquelle la face non galvanisée est arrosée de liquide de décapage et la face galvanisée est arrosée d'eau, de manière homogène sur toute la largeur de la tôle, et traverse ensuite une zone de lavage (9) dans laquelle les deux faces sont arrosées d'eau, qui est ensuite évacuée par des rouleaux essoreurs (12), avant éventuellement de subir un nouveau rinçage à l'eau.
EP88890198A 1988-07-28 1988-07-28 Procédé de post-traitement chimique de surfaces de bandes en acier Expired - Lifetime EP0352399B1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
DE8888890198T DE3871143D1 (de) 1988-07-28 1988-07-28 Verfahren zur chemischen nachbehandlung von stahlblechoberflaechen.
EP88890198A EP0352399B1 (fr) 1988-07-28 1988-07-28 Procédé de post-traitement chimique de surfaces de bandes en acier
ES198888890198T ES2033017T3 (es) 1988-07-28 1988-07-28 Procedimiento para el tratamiento de chapas de acero cincadas electroliticamente en un lado.
AT88890198T ATE76115T1 (de) 1988-07-28 1988-07-28 Verfahren zur chemischen nachbehandlung von stahlblechoberflaechen.
US07/387,080 US5043022A (en) 1988-07-28 1989-07-28 Method of treating a one-side electrogalvanized steel sheet

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP88890198A EP0352399B1 (fr) 1988-07-28 1988-07-28 Procédé de post-traitement chimique de surfaces de bandes en acier

Publications (2)

Publication Number Publication Date
EP0352399A1 EP0352399A1 (fr) 1990-01-31
EP0352399B1 true EP0352399B1 (fr) 1992-05-13

Family

ID=8200714

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88890198A Expired - Lifetime EP0352399B1 (fr) 1988-07-28 1988-07-28 Procédé de post-traitement chimique de surfaces de bandes en acier

Country Status (5)

Country Link
US (1) US5043022A (fr)
EP (1) EP0352399B1 (fr)
AT (1) ATE76115T1 (fr)
DE (1) DE3871143D1 (fr)
ES (1) ES2033017T3 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6277213B1 (en) 1996-12-06 2001-08-21 Siemens Aktiengesellschaft Surface treatment of steel or a nickel alloy and treated steel or nickel alloy

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2697032B1 (fr) * 1992-10-19 1995-01-06 Lorraine Laminage Procédé de décapage de matériaux en acier.
GB2273108B (en) * 1992-12-03 1997-06-04 Taiwan Galvanizing Co Ltd The method of adhering colored electroplating layer on a zinc-electroplated steel article
US6372706B1 (en) * 1996-10-04 2002-04-16 Henkel Corporation Alkaline hard surface cleaner and process therewith
US6126997A (en) * 1999-02-03 2000-10-03 Bulk Chemicals, Inc. Method for treating magnesium die castings
US6270620B1 (en) * 1999-09-14 2001-08-07 World Wiser Electronics Inc. Etching device
DE10156624B4 (de) * 2001-11-17 2005-10-27 Robert Bosch Gmbh Verfahren und Beizlösung zum Abreinigen von Belägen eines Stahl-Werkstückes
EP2094880B1 (fr) * 2007-02-12 2012-09-05 Henkel AG & Co. KGaA Procédé de traitement de surfaces métalliques

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3537926A (en) * 1967-06-19 1970-11-03 Lancy Lab Chemical brightening of iron-containing surfaces of workpieces
LU60299A1 (fr) * 1969-02-07 1970-04-06
FR2539140A1 (fr) * 1983-01-07 1984-07-13 Ugine Kuhlmann Stabilisation de solutions aqueuses contenant du peroxyde d'hydrogene, de l'acide fluorhydrique et des ions metalliques
US4452643A (en) * 1983-01-12 1984-06-05 Halliburton Company Method of removing copper and copper oxide from a ferrous metal surface
US4659605A (en) * 1984-05-16 1987-04-21 Richardson Chemical Company Electroless deposition magnetic recording media process and products produced thereby
EP0183894B1 (fr) * 1984-11-30 1991-07-24 Feldmann-Chemie GmbH Utilisation des mélanges d'acides et/ou de sels acides pour l'élimination de dépôts ou de taches de fer ou de manganèse
US4632733A (en) * 1985-12-30 1986-12-30 Nippon Kokan Kabushiki Kaisha Method for manufacturing one-side electrogalvanized steel strip
US4708779A (en) * 1986-10-20 1987-11-24 Bethlehem Steel Corporation Chemical post-treatment of selectively galvanized steel strip and sheet
JPS63172799A (ja) * 1987-01-12 1988-07-16 日本パ−カライジング株式会社 アルミニウムの表面洗浄剤

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6277213B1 (en) 1996-12-06 2001-08-21 Siemens Aktiengesellschaft Surface treatment of steel or a nickel alloy and treated steel or nickel alloy

Also Published As

Publication number Publication date
US5043022A (en) 1991-08-27
DE3871143D1 (de) 1992-06-17
ES2033017T3 (es) 1993-03-01
ATE76115T1 (de) 1992-05-15
EP0352399A1 (fr) 1990-01-31

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