EP1358367B1 - Decapage et decalaminage par voie electrolytique continue de l'acier au carbone et de l'acier inoxydable - Google Patents

Decapage et decalaminage par voie electrolytique continue de l'acier au carbone et de l'acier inoxydable Download PDF

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Publication number
EP1358367B1
EP1358367B1 EP01271468A EP01271468A EP1358367B1 EP 1358367 B1 EP1358367 B1 EP 1358367B1 EP 01271468 A EP01271468 A EP 01271468A EP 01271468 A EP01271468 A EP 01271468A EP 1358367 B1 EP1358367 B1 EP 1358367B1
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EP
European Patent Office
Prior art keywords
current
anodic
descaling
pickling
electrolytic
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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EP01271468A
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German (de)
English (en)
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EP1358367A1 (fr
Inventor
Susanna Centro Sviluppo Materiali S.p.A. RAMUNDO
A. Centro Sviluppo Materiali S.p.A. DULCETTI
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Centro Sviluppo Materiali SpA
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Centro Sviluppo Materiali SpA
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Priority claimed from IT2000RM000674 external-priority patent/IT1316027B1/it
Priority claimed from IT2000RM000675 external-priority patent/IT1316028B1/it
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Publication of EP1358367A1 publication Critical patent/EP1358367A1/fr
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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
    • C25F1/06—Iron or steel

Definitions

  • the present invention refers to the continuous pickling of hot-rolled carbon steels strips by an electrolytic process in a neutral solution (pH ranging from 6.0 to 8.0).
  • the present invention further refers to the field of the continuous descaling of stainless steels strip for the removal of surface oxides formed by effect of thermal treatments, comprising hot-rolling and annealing.
  • the advantages of the neutral electrolytic pickling and descaling processes with respect to the conventional processes in acid baths are substantially the following: adoption of non-dangerous, non-harmful and non-polluting pickling baths; easy treating and reclaiming of the residues; and elevated surface quality of the pickled materials.
  • the first reaction (0) is merely viable at a low electrode potential and it is marginal as a pickling reaction; it becomes virtually negligible for current density (I) values exceeding a predetermined threshold value (I 0 ).
  • reaction (1) acidifies the metal-scale interface
  • reaction (2) changes the scale into a soluble compound, by virtue of the presence of the acidified interface.
  • the anodic oxidation of the underlying metal begins to rise until reaching its equilibrium rate at the passive state, when all the scale has been removed from the surface (end of the pickling treatment). Therefore, under the electrolytic pickling mechanism defined by the second (1) and by the third (2) reaction the fourth reaction (3) is marginal.
  • auxiliary electrodes also called counterelectrodes
  • auxiliary electrodes onto which the cathodic reactions enabling the electric neutrality of the solution to be preserved take place.
  • reaction ratios depend on the diffusion of the reactants and of the reaction products through the boundary layer (flow), which in turn is determined by the fluid dynamics onto the steel surface.
  • flow the boundary layer
  • the increase in the burble of the solution at the interface can cause contrasting effects onto the attack rate of the scale, as it also increases the flow of Hydrogen ions (H + ) which leaves the interface acidified [reaction (1)].
  • descaling pre-treatments are carried out prior to the chemical pickling.
  • the function of the descaling is that of modifying the scale in order to facilitate the subsequent removal thereof.
  • the scale conditioning methods for hot-rolled stainless steel strips mainly use molten salt baths (thermochemical descaling) or electrolytic treatments.
  • thermochemical process currently used for descaling provides the immersion in an oxidising molten salt bath which is capable of converting the Chromium oxides (or the mixed Chromium/Iron oxides) into soluble hexavalent Chromium compounds.
  • Electrolytic descaling is a common industrial process which can be carried out in acid electrolytes as well as in neutral electrolytes, the anion usually being the sulfate ion. Particularly attractive is the process of electrolytic descaling in a neutral solution. In fact, this type of descaling is effective in dissolving the scale and the removed scale is directly separated from the solution by precipitation, with no need of a residue treatment (e.g., by neutralizing). Moreover, for the construction of the plant no material particularly resistant to corrosion is required.
  • auxiliary electrodes or counterelectrodes
  • the cathodic reactions enabling the electrical neutrality of the solution to be preserved develop.
  • reaction (7) merely applies to austenitic stainless steels, as ferritic stainless steels do not contain appreciable quantities of Nickel as an alloy metal.
  • the resulting electrolytic descaling mechanism in a neutral solution involves the anodic oxidation of the Chromium and the interface acidification, which determines the dissolving of the Iron oxide, and, when present, of the Nickel oxide.
  • the anodic oxidation of the underlying metal begins to increase, until reaching its equilibrium rate at the passive state, according to the following schematic reaction: Me + nH 2 O ⁇ MeO n + 2nH + + 2ne - where Me indicates the Fe-Cr-Ni alloy; then, only the reactions (1) and (5) take place, the latter however at a much slower rate with respect to the former.
  • reaction ratios depend on the diffusion of the reactants and of the reaction products through the boundary layer, which in turn is determined by the fluid dynamics onto the steel surface.
  • the increase in the burble of the solution at the interface can cause contrasting effects onto the attack rate of the scale, as it also increases the flow of H + which leaves the interface acidified [reaction (1)].
  • the quantity of a substance obtained (changed) at the electrodes is proportional to the quantity of electric charge passed through the electrolytic circuit. More particularly, the quantity of electric charge required to obtain (change) a given quantity of substance is constant (e.g., for one equivalent of any substance one Faraday, i.e. 96.500 Coulomb, is required). Hence, for the electrolytic change of a given quantity of substance, the associated current density is constant.
  • the present invention meets this demand, further providing additional advantages which will hereinafter be made apparent.
  • an object of the present invention is a continuous electrolytic method in a neutral solution for the pickling and the descaling of carbon steels and stainless steels according to claim 1.
  • the neutral saline solution preferably consists of sodium sulfate, in a concentration from 0,5 to 2,5 M, at a temperature ranging from 30 to 100°C.
  • Treatment times range from 7 to 50 s for Carbon steels and from 2 to 45 s for stainless steels.
  • Current density ranges from 10 to 80 A/dm 2 (Carbon steels) and from 5 to 150 A/dm 2 (stainless steels).
  • the anodic treatment time depends on the line speed (v) and on the total length of the electrodes (L) which give the anodic polarization to the strip to be processed.
  • another object of the present invention is the use of the abovedescribed electrolytic method, characterised in that, setting the width and the flow rate of the strip, the total anodic electrode length, and therefore the length of the related continuous neutral electrolytic treatment line, the current to be outputted, selected according to the abovedescribed method and defined according to claims 4 and 8.
  • the electrolytic treatment of steel strips is usually carried out in cells consisting of a set of electrodes connected to opposite poles of the power supplies, which determine alternatively anodic and cathodic polarization sequences onto the strip to be descaled.
  • the descaling process merely requires the anodic polarization
  • the addition of the cathodic stage entails the advantage of having the electrochemical reactions take place directly onto the strip, with no direct connection of the latter to the power supplies; thus, the employ of costly current carrier rolls can be avoided.
  • the total length (L) of the electrodes imposing the anodic polarization onto the strip is given by the sum of the unitary lengths (L a ) of the individual electrode units.
  • the cell may have a vertical or a horizontal development, according to plant convenience criteria.
  • This frequency limit value for the electrolytic pickling in a neutral solution is compatible with the reaction mechanisms advanced for the treatment, implying the acidification of the electrified interface in order to foster the dissolving of the oxides.
  • Adopting e.g., hot-rolled Carbon steels strips under predetemined industrial conditions (with constant post-rolling cooling modes)
  • the scale obtained exhibits a near-constant composition and morphology, requiring in order to be electrolytically pickled a minimum charge quantity c, depending on the pre-pickling scale-breaking mechanical treatment.
  • a common low-Carbon steel having hot-rolling scale mechanically pre-conditioned by roll-induced squashing (about 2.5% lengthening) is subjected to the continuous electrolytic pickling method in a neutral solution according to the present invention.
  • the total anodic electrode length (L), and therefore the length of the pickling plant are set with regard to the current applied in the cell according to the provisions of the equation of the neutral electrolytic pickling according to the present invention.
  • the current density (I) to be applied to the electrolytic pickling cell as a function of the anodic electrode length (L) and of the varying of the line speed (v) is reported in column 3 of Table 1; in column 4 the electric charge density (Q), and in column 5 the total current (I tot ) to be outputted, calculated multiplying the current density for the anodic electrode surface, are indicated.
  • the electric charge density (Q) to be outputted for the electrolytic pickling increases when the anodic electrode length decreases.
  • the total current (I tot ) applied increases.
  • the slow-speed (20 m/min) operation implies the employ of a total anodic length not exceeding 16 m, lest the condition that I>I 0 be not met. This is attained by sectioning the electrodes and power-supplying only a section thereof, regardless of the total length of the anodes installed in the cells.
  • the total anodic electrode length (L), and therefore the length of the pickling plant are set with regard to the current applied in the cell, according to the provisions of the equation of continuous neutral electrolytic pickling according to the invention.
  • the former should be capable of operating at a speed ranging from 40 to 120 m/min, according to two different process control logics: in the one case (see Table 4a) with the logic of maximising the use of the power from the individual power supplies (i.e., use of a number of cells proportional to the line speed) and, in the other case (see Table 4b), with the constant employ of all the cells (i.e., use of a current density proportional to the line speed).
  • the direct current density (I) to be applied to the electrolytic pickling cell at the variation of the line speed (v) is reported in column 2 of Table 5; in column 3 the electric charge density (Q), and in column 4 the total current (I tot ) to be outputted, calculated multiplying the current density for the anodic electrode surface, are indicated.
  • the operative parameters of this plant, calculated with the descaling equation according to the invention, are reported in Table 6.
  • the operative parameters of this plant, calculated by the descaling equation according to the invention are reported in Table 7.
  • the two process control logics are not equivalent, as overall lesser total descaling currents are required when operation is carried out maximising the number of cells employed. In this case as well, the underrating of the descaling current by the classical equation of electrolysis persists.

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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)
  • Electroplating Methods And Accessories (AREA)
  • Electrolytic Production Of Metals (AREA)

Claims (10)

  1. Procédé électrolytique continu dans une solution neutre pour le décapage et le décalaminage d'aciers au carbone et d'aciers inoxydables, en présence d'effets indirects de circulation de courant d'électrolyse, ledit courant étant un courant continu ou un courant alternatif, ayant une fréquence inférieure à 3 Hz, dans lequel le temps de traitement anodique, lorsque le courant de cellule voulu est appliqué, et le courant de cellule, lorsque le temps de traitement voulu est adopté, sont sélectionnés conformément à la formule suivante : It = C + kI où
    I est la densité de courant traversant la cellule,
    t est le temps de traitement anodique,
    c est la fraction constante de densité de charge électrique délivrée en sortie pour les réactions anodiques de changement d'oxyde directes,
    k est une constante de temps pour le calcul de la fraction de densité de charge électrique, proportionnelle à la densité de courant I (kI), délivrée en sortie pour les réactions anodiques indirectes liées à un développement d'oxygène et à l'acidification conséquente au niveau de l'interface acier/solution électrolytique, pour les aciers au carbone, et au niveau de l'interface calamine/solution pour les aciers inoxydables,
       les constantes c et k étant connues pour chaque type d'acier et chaque type de calamine.
  2. Procédé électrolytique continu dans une solution neutre, en présence d'effets indirects de circulation de courant d'électrolyse, ledit courant étant un courant continu ou un courant alternatif, ayant une fréquence inférieure à 3 Hz, selon la revendication 1, dans lequel la solution neutre est constituée de préférence de sulfate de sodium, selon une concentration allant de 0,5 à 2,5 M, à une température dans le plage de 30 à 100°C.
  3. Procédé électrolytique continu dans une solution neutre pour le décapage d'aciers au carbone, en présence d'effets indirects de circulation de courant continu d'électrolyse, selon la revendication 1 ou 2, dans lequel la quantité de charge électrique c se trouve dans la plage de 200 à 1250 C/dm2 et la constante de temps k se trouve dans la plage de 2 à 11 s, pour des temps de traitement anodique dans la plage de 7 à 50 s et une densité de courant dans la plage de 10 à 80 A/dm2.
  4. Utilisation du procédé électrolytique continu dans une solution neutre pour le décapage d'aciers au carbone, en présence d'effets indirects de circulation de courant d'électrolyse, ledit courant étant un courant continu ou un courant alternatif ayant une fréquence inférieure à 3 Hz, selon l'une quelconque des revendications 1 à 3, caractérisée en ce que, lors de l'établissement de la largeur de la bande à décaper, de la vitesse v de la bande à décaper et du courant de cellule I, la longueur d'électrode anodique totale, et par conséquent la longueur L de la ligne de décapage électrolytique neutre continue apparentée, est définie par la formule suivante : I = c/(L/v - k) qui est la formule de la revendication 1 réécrite en remplaçant le temps t par le rapport L/v.
  5. Utilisation selon la revendication 4, dans laquelle une logique de commande de traitement fournissant l'utilisation d'un nombre de cellules proportionnel à la vitesse de ligne et l'utilisation de la puissance maximale disponible, est adoptée.
  6. Utilisation selon la revendication 4, dans laquelle une logique de commande de traitement fournissant l'utilisation constante de toutes les cellules et l'utilisation d'une densité de courant proportionnelle à la vitesse de ligne, est adoptée.
  7. Procédé électrolytique continu dans une solution neutre pour le décalaminage d'aciers inoxydables, en présence d'effets indirects de circulation de courant continu d'électrolyse, selon la revendication 1 ou 2, dans lequel la quantité de charge électrique c se trouve dans la plage de 40 à 200 C/dm2 et la constante de temps k se trouve dans la plage de 2 à 25 s, pour des temps de traitement anodique dans la plage de 2 à 45 s et des densités de courant dans la plage de 5 à 150 A/dm2.
  8. Utilisation du procédé de décalaminage électrolytique continu d'aciers inoxydables dans une solution neutre, en présence d'effets indirects de circulation de courant d'électrolyse, ledit courant étant un courant continu ou un courant alternatif, ayant une fréquence inférieure à 3 Hz, selon les revendications 1, 2 ou 7, caractérisée en ce que, lors de l'établissement de la largeur et de la vitesse v' de la bande à décalaminer et du courant de cellule I', la longueur d'électrode anodique totale, et par conséquent la longueur L' de la ligne de décalaminage neutre électrolytique continue apparentée, est définie par la formule suivante : I' = c'/(L'/v' - k') qui est la formule de la revendication 1 réécrite en remplaçant le temps t' par le rapport L'/v'.
  9. Utilisation du procédé selon la revendication 8, dans laquelle une logique de commande de traitement fournissant l'utilisation d'un nombre de cellules proportionnel à la vitesse de ligne et l'utilisation de la puissance maximale disponible, est adoptée.
  10. Utilisation du procédé selon la revendication 9, dans laquelle une logique de commande de traitement fournissant l'utilisation constante de toutes les cellules et l'utilisation d'une densité de courant proportionnelle à la vitesse de ligne, est adoptée.
EP01271468A 2000-12-18 2001-12-18 Decapage et decalaminage par voie electrolytique continue de l'acier au carbone et de l'acier inoxydable Expired - Lifetime EP1358367B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
IT2000RM000674 IT1316027B1 (it) 2000-12-18 2000-12-18 Metodo per il decapaggio elettrolitico continuo in soluzione neutra di acciaio al carbonio in presenza di effetti indiretti del passaggio di
ITRM20000674 2000-12-18
ITRM20000675 2000-12-18
IT2000RM000675 IT1316028B1 (it) 2000-12-18 2000-12-18 Metodo per la descagliatura elettrolitica continua in soluzione neutra di acciai inossidabili in presenza di effetti indiretti del passaggio
PCT/IT2001/000637 WO2002050344A1 (fr) 2000-12-18 2001-12-18 Decapage et decalaminage par voie electrolytique continue de l'acier au carbone et de l'acier inoxydable

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EP1358367A1 EP1358367A1 (fr) 2003-11-05
EP1358367B1 true EP1358367B1 (fr) 2004-09-15

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EP01271468A Expired - Lifetime EP1358367B1 (fr) 2000-12-18 2001-12-18 Decapage et decalaminage par voie electrolytique continue de l'acier au carbone et de l'acier inoxydable

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EP (1) EP1358367B1 (fr)
KR (1) KR20030076589A (fr)
CN (1) CN1231615C (fr)
AT (1) ATE276386T1 (fr)
AU (1) AU2002217449A1 (fr)
DE (1) DE60105653T2 (fr)
ES (1) ES2232564T3 (fr)
WO (1) WO2002050344A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITRM20010223A1 (it) * 2001-04-24 2002-10-24 Ct Sviluppo Materiali Spa Metodo per la descagliatura elettrolitica continua di acciai inossidabili in presenza di effetti indiretti del passaggio di corrente.
IT1395853B1 (it) 2009-09-30 2012-10-26 Tenova Spa Gruppo di preparazione superficiale per linee di produzione di nastri metallici
ITMI20130493A1 (it) * 2013-03-29 2014-09-30 Tenova Spa Metodo per trattare in continuo la superficie di un laminato di acciaio inossidabile in una soluzione a base di acido solforico
CN104120438B (zh) * 2014-07-22 2016-04-20 中冶南方工程技术有限公司 一种热轧304奥氏体不锈钢带钢酸洗生产方法
CN106181586A (zh) * 2016-07-01 2016-12-07 陕西飞机工业（集团）有限公司 一种不锈钢焊缝或者弯折区域的防腐蚀方法
CN111020683A (zh) * 2019-11-22 2020-04-17 山西太钢不锈钢股份有限公司 一种不锈钢板带酸洗电解电流自动控制方法
EP4065754A1 (fr) 2019-11-25 2022-10-05 ArcelorMittal Décapage électro-assisté de l'acier

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4363709A (en) * 1981-02-27 1982-12-14 Allegheny Ludlum Steel Corporation High current density, acid-free electrolytic descaling process
JPH06158400A (ja) * 1992-11-24 1994-06-07 Nakagawa Boshoku Kogyo Kk 鋼材表面のスケール除去方法

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Publication number Publication date
CN1486373A (zh) 2004-03-31
EP1358367A1 (fr) 2003-11-05
KR20030076589A (ko) 2003-09-26
CN1231615C (zh) 2005-12-14
ATE276386T1 (de) 2004-10-15
DE60105653D1 (de) 2004-10-21
WO2002050344A1 (fr) 2002-06-27
DE60105653T2 (de) 2005-09-29
AU2002217449A1 (en) 2002-07-01
ES2232564T3 (es) 2005-06-01

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