EP1307609B1 - Procede de decapage electrolytique continu pour produits metalliques utilisant des cellules alimentees en courant alternatif - Google Patents

Procede de decapage electrolytique continu pour produits metalliques utilisant des cellules alimentees en courant alternatif Download PDF

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Publication number
EP1307609B1
EP1307609B1 EP01961136A EP01961136A EP1307609B1 EP 1307609 B1 EP1307609 B1 EP 1307609B1 EP 01961136 A EP01961136 A EP 01961136A EP 01961136 A EP01961136 A EP 01961136A EP 1307609 B1 EP1307609 B1 EP 1307609B1
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Prior art keywords
electrolytic
pickling method
concentration
acid
electrolytic pickling
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German (de)
English (en)
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EP1307609A2 (fr
Inventor
L. Centro Sviluppo Materiali S.p.A. PACELLI
V. Centro Sviluppo Materiali S.p.A. FERRARI
Stefano Centro Sviluppo Materiali S.p.A. LUPERI
Mauro Centro Sviluppo Materiali S.p.A. CAMPIONI
Bruno Centro Sviluppo Materiali S.p.A. FERRI
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Centro Sviluppo Materiali SpA
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Centro Sviluppo Materiali SpA
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
    • C25F1/02—Pickling; Descaling
    • C25F1/04—Pickling; Descaling in solution
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
    • C25F1/02—Pickling; Descaling
    • C25F1/04—Pickling; Descaling in solution
    • C25F1/06—Iron or steel

Definitions

  • the present invention relates to a continuous electrolytic pickling method for metallic products, in particular in Iron, Nickel, Titanium and alloys thereof, based on the use of alternate current supplied cells with electrolytic solution consisting of acid or neutral aqueous solutions.
  • pickling e.g. for the stainless steels
  • pickling is actually carried out in order to eliminate the scale of thermal oxides which are generated during the hot-rolling and/or annealing treatments, and to dissolve the Chromium-depleted alloy layer (dechromized layer) therebelow.
  • This conventional method consists of three conceptually different steps: a first step of descaling, i.e., physico-chemical modification of the scale with the partial removal thereof; a second step of actual pickling, i.e. removal and solution of the residual scale and disposal of the sub-surface layer of dechromized alloy; and a third step, so-called of finishing, consisting in a surface passivation.
  • the latter two steps are often carried out at the same time.
  • the step of descaling is carried out by sandblasting with a hard grit which breaks up and partially removes the scale.
  • the step of descaling cannot be carried out by surface peening, which is not compatible with the quality of the finished product's surface.
  • the pickling step is generally carried out using highly oxidizing acid baths, capable of dissolving the sub-surface alloy layer (Cr-depleted for stainless steels) determining the detachment of the scale adhering thereto.
  • electrolytic cells capable of applying a continuous current density ranging from 3 A/dm 2 to 40 A/dm 2 to the material are used.
  • the finishing step aimed at forming a passivated protective film, when this is not carried out at the same time as the pickling step, is usually attained in baths having high redox potential.
  • These baths contain the abovementioned acids and oxidizers at lower concentrations and with a lower content of the ions of the metals present in the metallic products to be pickled.
  • washing sections consisting of water jet systems equipped with rotary brushes are inserted.
  • the function carried out by these systems is the removal of the pickling solution dragged by the strip, and the non-adhering scale particles deposed on the strip surface.
  • DE-A-19624436, WO 9826111, EP-A-763609 and JP95-130582 disclose pickling processes in acid solution, free from nitric acid, in presence of ferric ions with the use of alternate current supplied electrolytic cells (current density comprised between 0.5 A/dm2 and 250 A/dm2).
  • DE-C-3937438 discloses a process in which direct current is employed for the reoxidation of the ferrous ions to ferric ions in a hydrochloric acid solution.
  • EP-A-838542 discloses a pickling process in an aqueous sodium sulphate solution, having a concentration between 10 g/l and 350 g/l, in which the strip is vertically passed between pairs of counter electrodes, a direct current having a density between 20 A/dm2 and 250 A/dm2 being applied therebetween.
  • the main drawback of the process for the mechanical removal of the scale by sandblasting or peening lies in the difficulty of abating the dusts made of silica and metallic oxides particles, not to mention the high noise pollution of the surrounding working areas.
  • the baths of sulphuric and of hydrofluoric acid which use, instead of the nitric acid, systems having a high redox potential, entail a complex management in connection with the difficulties of maintaining the appropriate concentrations of reagents capable of ensuring the envisaged pickling kinetics.
  • the costs of the reagents e.g., of the stabilised hydrogen peroxide, are high, considering that a fraction of the metals accumulating in the solution react with the oxidizers, lowering the process effectiveness.
  • the present invention allows to overcome all of the abovementioned drawbacks, further providing other advantages which will hereinafter be made apparent.
  • an object of the present invention is to provide a pickling method for continuously cast products in steel, in compliance of the UNI EU 74/20 norm, and in Nickel alloy and in Titanium, based on the use of alternate current supplied electrolytic cells in acid or neutral aqueous solutions.
  • an object of the present invention is a continuous electrolytic pickling method for steels, Nickel super alloys, Titanium and alloys thereof, characterised in that the material to be treated, for a time between 3 and 60 seconds, is immersed into or passes through at least one electrolytic cell with an electrolytic solution, free of nitric acid, consisting of a neutral or acid aqueous solution, at a temperature between 20°C and 95°C, with at least one pair of electrodes connected to an alternate current power supply having a frequency ranging from 40 Hz to 70 Hz, the electrolysis being carried out at a current density having an effective amplitude ranging from 10 A/dm2 to 250 A/dm2.
  • the electrolytic solution can be an aqueous solution, at a temperature between 20°C and 95°C, containing the following components having a concentration expressed in g/l:
  • the electrolytic solution is maintained at a temperature between 70°C and 90°C and comprises sulphuric acid at a concentration between 150 g/l and 250 g/l, and ferric ions (Fe +3 ) at a concentration of from 5 g/l to 40 g/l.
  • the electrolytic solution is at a temperature between 70°C and 90°C, and comprises sulphuric acid at a concentration between 150 g/l and 250 g/l and at least one between hydrofluoric acid at a concentration between 5 g/l and 50 g/l and hydrochloric acid at a concentration between 5 g/l and 50 g/l.
  • the electrolytic solution is at 70°C-90°C and comprises sulphuric acid at a concentration between 150 g/l and 250 g/l.
  • the electrolytic solution may be a sodium sulphate (Na 2 SO 4 ) neutral aqueous solution having a concentration ranging from 25 g/l to 300 g/l at a temperature between 50°C and 95°C.
  • Na 2 SO 4 sodium sulphate
  • pairs of adjacent electrodes are connected to two separate power supplies, so that the current lines outputted from a first electrode pair facing one side of the material to be treated, cross said material and close again on a second electrode pair, opposed to the first one and facing the other side of the material to be treated, defining a substantially X-shaped course.
  • electrodes facing one side of the material to be treated are connected to a power supply, so that the current lines which are outputted from said electrodes and cross the material, close again on other electrodes opposed to the first ones and facing the opposite side of the material to be treated, defining a course which is substantially orthogonal to said sides.
  • the electrolytic pickling method according to the invention can be used for inducing a physical-chemical modification of the scale of the metallic oxides present onto the surface of the material to be pickled, a physical-chemical modification which, in the case of the stainless steels, occurs in a treatment time comprised between 1 sec and 10 sec.
  • the continuous electrolytic pickling method according to the present invention may be used in a step subsequent to that of the physical-chemical modification of the scale of metallic oxides present onto the surface of the material to be pickled.
  • this application of the pickling method according to the invention requires treatment times between 2 sec and 15 sec.
  • the electrolytic cells employable in the present invention may be vertical electrode or horizontal electrode cells, the former ones being preferable for the easy scavenging of the gas evolved by electrochemical reaction at made circuit.
  • the electrodes are made in materials resistant to the corrosive action of the baths employed.
  • the electrodes in the individual cell are connectable according to at least three schemes, reported by way of a non-limiting example in the attached Figs. 2, 3 and 4.
  • the electrodes may consist of an individual toroidal ring.
  • Another object of the present invention are the electrolytic cells characterised in that they have an electrode connection as indicated hereinafter and claimed in claims 8 and 9.
  • the AC flow induces an over voltage of the free corrosion potential on the surface of the alloy to be pickled, so as to reach thereon electrochemical potentials capable of fostering several oxidation-reduction reactions which involve both the alloy and the oxide layer thereabove, as well as the aqueous solution.
  • the dissolved Iron, in form of ferrous ion deriving from the solution of steel, is capable of fostering the reduction, according to the abovedescribed reaction, of all the Cr (VI) ions to Cr (III) ions, so that the Cr (VI) ions be absent from the solution.
  • the voltage-current phase displacement assessed by electrode impedance spectroscopy, is such that at frequencies between 40 Hz and 70 Hz more than 90% of the current crossing the cell is in phase with the applied voltage (active component of the current) and it allows the abovementioned electrochemical reactions.
  • a mere 10% of the current is shifted 90° out of phase with respect to the voltage (reactive component of the current) it being employed, for the load, the discharge of the pseudo-condenser made by the double electric charge layer on the electrode surface.
  • the active component tends to decrease in favour of the reactive one, decreasing the fraction of the current fostering the electrochemical reactions required for the pickling.
  • the solution kinetics of the alloys to be pickled are high, particularly so, considering that the oxide is in no way pre-treated or conditioned prior to the in-cell electrolytic treatment.
  • Figure 1 shows the progress of the weight loss expressed in g/m 2 as a function of the time for the entire pickling treatment in a 200 g/l H 2 SO 4 aqueous solution for a X 6 CrTi 12 (AISI 409) cold-rolled and annealed steel.
  • Figure 2 shows a first electrode configuration, in which electrodes 1 located at the same side of the strip N are alternately connected to the two terminals of a phase of a transformer.
  • the electrodes 2 located at the side opposed to the strip are connectable to the same terminal of a phase of a transformer, connecting them to the corresponding ones on the other side.
  • Figure 3 shows a second configuration in which the electrodes 1 located in the same side of strip N are connected to the same terminal of one or more phases of one or more transformers, and the opposed electrodes 2 are connected to the other terminal of the corresponding phases of the transformers.
  • the current is applied with the electrode configuration shown in figure 2.
  • the interelectrode gap is equal to 80 mm.
  • the in-tank solution is such as to maintain with the immersed strip surface a ratio not lower than 1m 3 solution/m 3 strip and it is renewed upon reaching the limits set for the dissolved metals.
  • the treatment time i.e., the period in which the material is subjected to the action of the alternate current, was set at 15 sec, in connection with the strip speed and the electrode sizes.
  • the weight loss attained at the end of the treatment was equal to about 40 g/m 2 of strip.
  • Figure 1 shows the diagram related to the weight losses of the steel subject of the example as a function of the treatment time and for two different current densities applied.
  • the current was applied with the electrode configuration shown in figure 2.
  • the interelectrode gap is equal to 80 mm.
  • the in-tank solution is such as to maintain with the immersed strip surface a ratio not lower than 1m 3 solution/m 2 strip and it is renewed upon reaching the limits set for the dissolved metals.
  • the treatment time i.e., the period in which the material is subjected to the action of the alternate current, was set at between 5 sec and 25 sec, in connection with the strip speed and the electrode sizes
  • the weight loss attained at the end of the treatment was equal to about 40 g/m 2 of strip.

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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)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Electrolytic Production Of Metals (AREA)

Claims (14)

  1. Procédé de décapage électrolytique continu pour des aciers, superalliages de Nickel, Titane et alliages de celui-ci, caractérisé en ce que le matériau à traiter, pendant un temps compris entre 3 secondes et 60 secondes, est immergé ou passe à travers au moins une cellule électrolytique ayant une solution électrolytique, exempt d'acide nitrique, constituée d'une solution aqueuse neutre ou acide, comportant de l'acide sulfurique entre 20 et 300 g/l à une température comprise entre 20°C et 95°C, avec au moins une paire d'électrodes connectées à une alimentation en courant alternatif ayant une fréquence dans la plage allant de 40 Hz à 70 Hz, l'électrolyse étant effectuée à une densité de courant ayant une amplitude efficace dans la plage allant de 10 A/dm2 à 250 A/dm2.
  2. Procédé de décapage électrolytique selon la revendication la revendication 1, dans lequel la solution électrolytique est une solution aqueuse, à une température comprise entre 20°C et 95°C, contenant les composants suivants ayant des concentrations exprimées en g/l :
    acide sulfurique (H2SO4) entre 20 et 300, et au moins un élément parmi
    acide hydrofluorique (HF) entre 5 et 50
    acide orthophosphorique (H3PO4) entre 5 et 200
    ion ferrique (Fe+3) entre 5 et 40.
  3. Procédé de décapage électrolytique pour des aciers inoxydables selon l'une quelconque des revendications 1 à 2, dans lequel la solution électrolytique est maintenue à une température comprise entre 70°C et 90°C et comporte de l'acide sulfurique à une concentration comprise entre 150 g/l et 250 g/l, et des ions ferriques (Fe+3) à une concentration allant de 5 g/l à 40 g/l.
  4. Procédé de décapage électrolytique pour des superalliages à base de Nickel et pour du Titane des alliages de celui-ci selon la revendication 1 ou 2, dans lequel la solution électrolytique est maintenue à une température comprise entre 70 et 90°C et comporte de l'acide sulfurique à une concentration comprise entre 150 g/l et 250 g/l et au moins un élément parmi l'acide hydrofluorique à une concentration comprise entre 5 g/l à 50 g/l et l'acide chlorhydrique à une concentration comprise entre 5 g/l à 50 g/l.
  5. Procédé de décapage électrolytique pour de l'acier carboné selon l'une quelconque des revendications 1 à 2, dans lequel la solution électrolytique est maintenue entre 70°C et 90°C, et comporte de l'acide sulfurique à une concentration comprise entre 150 g/l et 250 g/l.
  6. Procédé de décapage électrolytique selon la revendication 1, dans lequel la solution électrolytique est une solution aqueuse de sulfate de sodium (Na2SO4) ayant une concentration dans la plage allant de 25 g/l à 300 g/l à une température comprise entre 50°C et 95°C.
  7. Procédé de décapage électrolytique selon l'une quelconque des revendications 1 à 6, dans lequel des paires d'électrodes adjacentes sont connectées à deux alimentations séparées, de sorte que les lignes de courant, qui sortent d'une première paire d'électrodes faisant face à un côté du matériau à traiter, traversent ledit matériau et se raccordent à nouveau sur une seconde paire d'électrodes, opposées à la première paire d'électrodes et faisant face à l'autre côté du matériau à traiter, définissant un trajet en forme essentiellement de X.
  8. Procédé de décapage électrolytique selon l'une quelconque des revendications 1 à 6, dans lequel des électrodes faisant faces à un côté du matériau à traiter sont connectées à une alimentation, de sorte que les lignes de courant, qui sortent desdites électrodes et traversent le matériau, se raccordent à nouveau sur d'autres électrodes opposées aux premières et faisant faces au côté opposé du matériau à traiter, définissant un trajet qui est essentiellement orthogonal auxdits côtés du matériau à traiter.
  9. Utilisation du procédé de décapage électrolytique selon les revendications 1 à 8, pour induire une modification physico-chimique de l'échelle des oxydes métalliques présents sur la surface du matériau à décaper.
  10. Utilisation du procédé de décapage électrolytique selon la revendication 9, pour des aciers inoxydables, ayant un temps de traitement compris entre 1 et 10 secondes.
  11. Utilisation du procédé de décapage électrolytique selon les revendications 1 à 8, dans une étape ultérieure à celle de la modification physico-chimique de l'échelle d'oxydes métalliques présents sur la surface du matériau à décaper.
  12. Utilisation du procédé de décapage électrolytique selon la revendication 11, dans une étape ultérieure à celle de la modification physico-chimique de l'échelle d'oxydes métalliques présents sur la surface du matériau à décaper, pour des aciers inoxydables, ayant un temps de traitement compris entre 2 secondes et 15 secondes.
  13. Utilisation du procédé de décapage selon les revendications 1 à 12, combinée à d'autres systèmes de décapage classiques.
  14. Piles électrolytiques, caractérisées en ce qu'elles ont une connexion d'électrode comme indiqué dans la revendication 7 ou la revendication 8.
EP01961136A 2000-08-10 2001-08-06 Procede de decapage electrolytique continu pour produits metalliques utilisant des cellules alimentees en courant alternatif Expired - Lifetime EP1307609B1 (fr)

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ITRM20000456 2000-08-10
IT2000RM000456A IT1317896B1 (it) 2000-08-10 2000-08-10 Metodo di decapaggio elettrolitico continuo di prodotti metallici concelle alimentate a corrente alternata.
PCT/IT2001/000435 WO2002012596A2 (fr) 2000-08-10 2001-08-06 Procede de decapage electrolytique continu pour produits metalliques utilisant des cellules alimentees en courant alternatif

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EP1307609A2 EP1307609A2 (fr) 2003-05-07
EP1307609B1 true EP1307609B1 (fr) 2004-03-17

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US (1) US20040031696A1 (fr)
EP (1) EP1307609B1 (fr)
CN (1) CN1318652C (fr)
AT (1) ATE262057T1 (fr)
AU (1) AU2001282513A1 (fr)
DE (1) DE60102387T2 (fr)
ES (1) ES2220795T3 (fr)
IT (1) IT1317896B1 (fr)
WO (1) WO2002012596A2 (fr)

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CN107525061A (zh) * 2017-08-23 2017-12-29 大唐东北电力试验研究所有限公司 一种火电厂锅炉炉管垢量测定系统及方法
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CN110512217A (zh) * 2019-09-23 2019-11-29 中冶南方工程技术有限公司 一种冷轧201奥氏体不锈钢无硝酸酸洗工艺
CN110528009A (zh) * 2019-09-23 2019-12-03 中冶南方工程技术有限公司 一种冷轧304奥氏体不锈钢无硝酸酸洗工艺
KR102286367B1 (ko) * 2019-11-11 2021-08-05 주식회사 포스코 고분자 연료전지 분리판용 스테인리스강의 제조방법
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KR102497442B1 (ko) * 2020-11-25 2023-02-08 주식회사 포스코 접촉저항이 향상된 고분자 연료전지 분리판용 오스테나이트계 스테인리스강 및 그 제조 방법
CN113788520A (zh) * 2021-10-08 2021-12-14 北京首钢吉泰安新材料有限公司 一种铁铬铝酸洗的工艺及废水处理方法和废水处理装置

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WO2002012596A3 (fr) 2002-04-25
US20040031696A1 (en) 2004-02-19
EP1307609A2 (fr) 2003-05-07
DE60102387T2 (de) 2005-03-24
WO2002012596A9 (fr) 2002-11-28
CN1318652C (zh) 2007-05-30
ES2220795T3 (es) 2004-12-16
AU2001282513A1 (en) 2002-02-18
ITRM20000456A1 (it) 2002-02-10
CN1451058A (zh) 2003-10-22
ATE262057T1 (de) 2004-04-15
WO2002012596A2 (fr) 2002-02-14
DE60102387D1 (de) 2004-04-22
ITRM20000456A0 (it) 2000-08-10
IT1317896B1 (it) 2003-07-15

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