EP0501867B1 - Verfahren zum Beizen von Stahlwerkstoffen wie z.B. rostfreien und legierten Stählen - Google Patents

Verfahren zum Beizen von Stahlwerkstoffen wie z.B. rostfreien und legierten Stählen Download PDF

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Publication number
EP0501867B1
EP0501867B1 EP92400471A EP92400471A EP0501867B1 EP 0501867 B1 EP0501867 B1 EP 0501867B1 EP 92400471 A EP92400471 A EP 92400471A EP 92400471 A EP92400471 A EP 92400471A EP 0501867 B1 EP0501867 B1 EP 0501867B1
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EP
European Patent Office
Prior art keywords
bath
acid
concentration
iron
steels
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
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EP92400471A
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English (en)
French (fr)
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EP0501867A1 (de
Inventor
Dominique Henriet
René Ledey
Didier Paul
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USINOR SA
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USINOR SA
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Publication of EP0501867A1 publication Critical patent/EP0501867A1/de
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    • 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
    • C23G1/086—Iron or steel solutions containing HF
    • 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

Definitions

  • the present invention relates to a method of pickling and descaling of stainless steel materials and / or alloy steel, and in particular over-stripping allowing elimination of an internal oxidation layer located on the surface of the materials, under the scale.
  • the oxidation layer internal is formed when the solubility of oxygen is very low, about 100 ppm, at particularly low partial pressure below the scale, on the surface of the metals or metal alloys.
  • the internal oxidation results in the formation of oxides of the residual or addition elements, more oxidizable than iron such as aluminum and / or silicon, these elements entering into the formation. of compounds such as iron aluminate (FeAl 2 O 4 ), the formation of these compounds being detrimental to the good performance of the materials in service.
  • iron aluminate FeAl 2 O 4
  • the oxidation of the material before pickling as a result of more or less weathering significant of the underlying metal or metal alloy generates surface dechromination thereafter a modification, in composition, of the healthy metal.
  • the products are immersed in over-pickling baths composed of nitric acid and hydrofluoric acid in a proportion of 60 to 160 g / l of HNO 3 and 10 to 50 g / l of HF, the overblasting bath being used at a temperature above 40 ° C.
  • Such a method allows, in use at a temperature above 60 ° C, the pickling of the layer affected by internal oxidation.
  • This process has the drawback, on the one hand, of lead to intense release of oxide vapor or particularly toxic nitrogen dioxide and, on the other hand, to generate releases of compounds nitrates, some of which are particularly toxic.
  • FR-A-2 587 369 also describes a pickling process for stainless steel products in which a compound pickling bath is used essentially a hydrofluoric acid bath and of water, in a concentration of less than 50 g / l in which dissolves iron into ferric iron and iron ferrous and the ferric iron content is maintained at at least 15 g / l by oxidation of the bath.
  • the active pickling agent is the ferric ion Fe 3+ , the acid solution containing H + ions being essentially a vector allowing maintenance in proportion of the ions Fe 2+ and Fe 3+ in the form of complexes, by controlling the redox potential of said pickling bath.
  • This process has the disadvantage, when the product surface is sensitive to the formation of a internal oxidation layer, for example during a long-term annealing, not to eliminate this layer.
  • GB-A-2 000 196 describes a pickling process at 50 ° C with a solution containing 5% hydrofluoric acid, 50 g / l ferric sulfate and 30 g / l ferrous sulfate and maintaining the potential oxidation-reduction of the bath to a value of +300 mV per addition of hydrogen peroxide and acid to the bath sulfuric.
  • the subject of the invention is a method of pickling of metallic materials such as steels stainless and alloy steels allowing in addition to pickling of calamines, a controlled over-stripping of a internal oxidation layer.
  • Maintaining the desired value of the redox potential can be obtained by introduction or in situ training in the bath an oxidizing gas chosen from air, ozone, oxygen or by adding compounds to the bath chosen from hydrogen peroxide, persalts, mineral and organic peracids, or any other oxygen source.
  • an oxidizing gas chosen from air, ozone, oxygen or by adding compounds to the bath chosen from hydrogen peroxide, persalts, mineral and organic peracids, or any other oxygen source.
  • the concentration of ferric iron (which found in complexed state) is usually 20 to 100 g / l.
  • the bath temperature is from 40 to 80 ° C.
  • FIG. unique represents the sectional image of an oxide layer on which the different compounds of constitution.
  • Fig. single is shown in section an oxide layer.
  • the various constituent compounds which are present there demonstrate the influence of oxygen and its partial pressure on the chemical form of said compounds.
  • a layer 2 of Fe 2 O 3 of a layer 3 of Fe 3 O 4 , of a layer 4 of FeO.
  • this set forming the oxide layer also called calamine, there sometimes appears a so-called internal oxidation layer which has a composition close to that of healthy metal, but which is enriched with inclusive oxidized compounds.
  • elements of this internal oxidation layer releases elements of constitution such as silicon and aluminum, very sensitive to oxygen, which forms compounds, such as, for example, iron silicates and aluminates, ( SiO 2 , 2FeO); (Al 2 O 3 , 3FeO).
  • control of these parameters is ensured in particular, on the one hand, by measuring a potential REDOX and, on the other hand, by the release of hydrogen.
  • the Fe +++ / Fe ++ ratio is maintained at a value between 1 and 10 and preferably at a value of 4 by measuring the REDOX potential maintained at 200 mV / Ag / AgCl.
  • the amount of hydrogen resulting from reaction (b) is 2 ml / cm 2 .
  • Hydrofluoric acid is introduced into the bath to maintain a concentration of 80 g / l.
  • the acid concentration is a determining factor in the over-stripping reaction, because it generates H + ions, complexing Fe +++ and Cr +++ ions, protruding and dissolving agent of the silicates present in the layer of internal oxidation.
  • the mixed complexes formed between Fe ++ and Fe +++ are of the Fe 2 F 5 nH 2 O type, n being between 2 and 10.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Pressure Welding/Diffusion-Bonding (AREA)
  • ing And Chemical Polishing (AREA)

Claims (6)

  1. Verfahren zum Beizen von Strahlwerkstoffen wie z.B. rostfreien und legierten Stählen, das die Beseitigung einer inneren Oxidationsschicht durch Überbeizen ermöglich, dadurch gekennzeichnet, daß man den Werkstoff in einem Bad behandelt, welches
    Fluorwasserstoffsäure (d = 1,25) in einer Konzentration von 80 bis 150 g/l
    Eisen(III) - Ionen in einer Konzentration von mindestens 20 g/l
    enthält, und daß man die Reaktionsbedingungen derart regelt, daß man gleichzeitig eine Reduktion von Eisen(III) zu Eisen(II) und eine Auflösungsreaktion der Metallelemente der Matrize des Werkstoffs hat, indem man das Bad bei einer Temperatur von 40 bis 80 °C ständig umrührt und das Redoxpotential des Bades bei einem Wert von 100 bis 350 mV gegenüber Ag/AgCl hält und eine derartige Säurekonzentraion aufrecht erhält, daß die Menge an freigesetztem Wasserstoff 0,1 bis 5 ml/cm2 Werkstoff beträgt (unter Normalbedingungen gemessen).
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man in dem Bad Einsen in einem Verhähltnis von 20 bis 100 g/l auflöst.
  3. Verfahren nach einem der Ansprüche 1 bis 2, dadurch gekennzeichnet, daß die Steuerung des erwünschten Wertes des Redoxpotentials durch Einleitung eines unter Luft, Ozon und Sauerstoff ausgewählten Oxidationsgases oder durch Bildung in situ in dem Bad erreicht wird.
  4. Verfahren nach einem der Ansprüche 1 bis 2, dadurch gekennzeichnet, daß die Steuerung des erwünschten Wertes des Redoxpotentials durch Zugabe von unter H2O2, Persalzen und mineralischen und organischen Persäuren ausgewählten Verbindungen in das Bad erreicht wird.
  5. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß das Volumen des Oxidationsgases zwischen 1 und 10 l/m2 Werkstoffoberfläche beträgt.
  6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man eine 40 volumenprozentige WasserstoffperoxidLösung in einer Menge von 10 bis 100 g/m2 Werkstoffoberfläche verwendet.
EP92400471A 1991-02-25 1992-02-24 Verfahren zum Beizen von Stahlwerkstoffen wie z.B. rostfreien und legierten Stählen Expired - Lifetime EP0501867B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9102222A FR2673200A1 (fr) 1991-02-25 1991-02-25 Procede de surdecapage de materiaux en acier tels que les aciers inoxydables et les aciers allies.
FR9102222 1991-02-25
US08/150,254 US5690748A (en) 1991-02-25 1993-11-10 Process for the acid pickling of stainless steel products

Publications (2)

Publication Number Publication Date
EP0501867A1 EP0501867A1 (de) 1992-09-02
EP0501867B1 true EP0501867B1 (de) 1999-01-07

Family

ID=26228531

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92400471A Expired - Lifetime EP0501867B1 (de) 1991-02-25 1992-02-24 Verfahren zum Beizen von Stahlwerkstoffen wie z.B. rostfreien und legierten Stählen

Country Status (9)

Country Link
US (1) US5690748A (de)
EP (1) EP0501867B1 (de)
AT (1) ATE175452T1 (de)
DE (1) DE69228080T2 (de)
DK (1) DK0501867T3 (de)
ES (1) ES2127208T3 (de)
FI (1) FI99031C (de)
FR (1) FR2673200A1 (de)
GR (1) GR3029688T3 (de)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1255655B (it) * 1992-08-06 1995-11-09 Processo di decapaggio e passivazione di acciaio inossidabile senza impiego di acido nitrico
DE4237021C1 (de) * 1992-11-02 1994-02-10 Poligrat Gmbh Mittel zum Beizen der Oberfläche von Chromnickelstählen und Chromstählen sowie Verwendung des Mittels
IT1276955B1 (it) 1995-10-18 1997-11-03 Novamax Itb S R L Processo di decapaggio e passivazione di acciaio inossidabile senza impiego di acido nitrico
US5724668A (en) * 1995-11-07 1998-03-03 Electronic Power Research Institute Method for decontamination of nuclear plant components
FR2745301B1 (fr) * 1996-02-27 1998-04-03 Usinor Sacilor Procede de decapage d'une piece en acier et notamment d'une bande de tole en acier inoxydable
US20040140288A1 (en) * 1996-07-25 2004-07-22 Bakul Patel Wet etch of titanium-tungsten film
IT1297076B1 (it) * 1997-11-24 1999-08-03 Acciai Speciali Terni Spa Metodo per il decapaggio di prodotti in acciaio
DE19755350A1 (de) * 1997-12-12 1999-06-17 Henkel Kgaa Verfahren zum Beizen und Passivieren von Edelstahl
GB9807286D0 (en) * 1998-04-06 1998-06-03 Solvay Interox Ltd Pickling process
USH2087H1 (en) * 1998-05-19 2003-11-04 H. C. Starck, Inc. Pickling of refractory metals
DE19833990A1 (de) * 1998-07-29 2000-02-10 Metallgesellschaft Ag Beizmittel für Edelstähle
EP1980650A1 (de) * 2007-04-05 2008-10-15 Kerma S.A. Nitrat- und Peroxydfreie Beizzusammensetzung und Verfahren zur Umsetzung einer solchen Zusammensetzung
CN109234746A (zh) * 2018-11-12 2019-01-18 江阴祥瑞不锈钢精线有限公司 一种不锈钢丝的酸洗工艺方法
US20220220619A1 (en) * 2020-01-09 2022-07-14 Primetals Technologies Japan, Ltd. Method for pickling steel plate and pickling apparatus
IT202000005848A1 (it) 2020-03-19 2021-09-19 Tenova Spa Processo per decapare e/o passivare un acciaio inossidabile.

Family Cites Families (21)

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US2474526A (en) * 1940-06-15 1949-06-28 Monsanto Chemicals Picking of stainless steels
US2337062A (en) * 1942-04-07 1943-12-21 Solar Aircraft Co Pickling solution and method
US2564549A (en) * 1945-07-02 1951-08-14 Albert R Stargardter Pickling treatment
US2856275A (en) * 1956-11-20 1958-10-14 Amchem Prod Chemical treatment of refractory metal surfaces
US3310435A (en) * 1963-11-18 1967-03-21 Dravo Corp Process for continuous pickling of steel strip and regeneration of the contact acid
AU471215B2 (en) * 1972-02-22 1976-04-15 Seat belt retractor
JPS549120A (en) * 1977-06-24 1979-01-23 Tokai Electro Chemical Co Method of controlling acid cleaning liquid for stainless steel
DE3105508A1 (de) * 1981-02-14 1982-09-02 Metallgesellschaft Ag, 6000 Frankfurt Beiz- und entrostungspaste fuer metalle
JPS5839234B2 (ja) * 1981-10-26 1983-08-29 住友金属工業株式会社 鋼線材の酸洗脱スケ−ル方法
US4608091A (en) * 1982-01-11 1986-08-26 Enthone, Incorporated Peroxide selective stripping compositions and method
DE3222532A1 (de) * 1982-06-16 1983-12-22 Arno 5042 Erftstadt Kuhlmann Verfahren und mittel zum sauren beizen von austenitischen edelstaehlen
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
FR2551465B3 (fr) * 1983-09-02 1985-08-23 Gueugnon Sa Forges Procede de decapage acide des aciers inoxydables et solution acide pour sa mise en oeuvre
FR2560893B1 (fr) * 1984-03-09 1986-09-12 Snecma Bain de decapage chimique pour pieces en alliage resistant a chaud
ATE121804T1 (de) * 1985-01-22 1995-05-15 Ugine Sa Verfahren zum säuren beizen von stahlen, insbesondere von rostfreien stahlen.
FR2587369B1 (fr) * 1985-09-19 1993-01-29 Ugine Gueugnon Sa Procede de decapage acide de produits en acier inoxydable
US5154774A (en) * 1985-09-19 1992-10-13 Ugine Aciers De Chatillon Et Gueugnon Process for acid pickling of stainless steel products
US5292374A (en) * 1988-11-15 1994-03-08 Maschinenfabrik Andritz Actiengesellschft Process and plant for pickling stainless steel strip
DE3937438C2 (de) * 1989-02-23 1998-01-29 Wilfried Simmer Verfahren zum Beizen von Stahl
FR2657888B1 (fr) * 1990-02-08 1994-04-15 Ugine Aciers Procedes de decapage de materiaux en acier inoxydable.
US5354383A (en) * 1991-03-29 1994-10-11 Itb, S.R.L. Process for pickling and passivating stainless steel without using nitric acid

Also Published As

Publication number Publication date
FR2673200A1 (fr) 1992-08-28
DE69228080T2 (de) 1999-05-20
FI99031C (fi) 1997-09-25
FR2673200B1 (de) 1995-03-03
EP0501867A1 (de) 1992-09-02
FI99031B (fi) 1997-06-13
DE69228080D1 (de) 1999-02-18
ES2127208T3 (es) 1999-04-16
ATE175452T1 (de) 1999-01-15
FI920787A (fi) 1992-08-26
US5690748A (en) 1997-11-25
DK0501867T3 (da) 1999-08-30
GR3029688T3 (en) 1999-06-30
FI920787A0 (fi) 1992-02-24

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