EP2978879B1 - Procédé de traitement en continu de la surface d'un stratifié en acier inoxydable dans une solution à base d'acide sulfurique - Google Patents

Procédé de traitement en continu de la surface d'un stratifié en acier inoxydable dans une solution à base d'acide sulfurique Download PDF

Info

Publication number
EP2978879B1
EP2978879B1 EP14722742.5A EP14722742A EP2978879B1 EP 2978879 B1 EP2978879 B1 EP 2978879B1 EP 14722742 A EP14722742 A EP 14722742A EP 2978879 B1 EP2978879 B1 EP 2978879B1
Authority
EP
European Patent Office
Prior art keywords
laminate
comprised
electrodes
solution
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.)
Active
Application number
EP14722742.5A
Other languages
German (de)
English (en)
Other versions
EP2978879A1 (fr
Inventor
Stefano Martines
Giovanni ASTENGO
Stefano Luperi
Luca Lattanzi
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.)
Tenova SpA
Original Assignee
Tenova SpA
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 Tenova SpA filed Critical Tenova SpA
Publication of EP2978879A1 publication Critical patent/EP2978879A1/fr
Application granted granted Critical
Publication of EP2978879B1 publication Critical patent/EP2978879B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F7/00—Constructional parts, or assemblies thereof, of cells for electrolytic removal of material from objects; Servicing or operating

Definitions

  • the present invention concerns a method for treating in continuous the surface of a laminate made of stainless steel in a solution based on sulfuric acid.
  • the method of the present invention is particularly suitable for treating a laminate made of stainless steel in order to remove the surface oxide layer (so-called "scale") which inevitably forms during the various heat treatments to which the laminate is subjected, including the hot lamination process itself.
  • scale surface oxide layer
  • the process for removing scale aims to remove both the outermost surface layer of metal oxide (richer in chrome with respect to the basic composition of steel) and the layer of alloy beneath it that, on the other hand, has a lower chrome content with respect to the base chemical composition of steel (dechromatized layer).
  • the pickling processes of the prior art generally provide three distinct steps.
  • the first step (descaling) a chemical-physical modification of the scale is induced in order to promote detachment from the laminate.
  • This step is carried out, for example, by immersing the manufactured product in baths of molten oxidizing salts, such as Kolene baths (mixtures of NaOH, NaNO 3 and NaCl) at temperatures around 500°C (thermochemical descaling), or electrolytically (electrolytic descaling) in neutral or acidic aqueous solutions (for example, aqueous solutions of sodium sulfate or sulfuric acid).
  • molten oxidizing salts such as Kolene baths (mixtures of NaOH, NaNO 3 and NaCl) at temperatures around 500°C (thermochemical descaling), or electrolytically (electrolytic descaling) in neutral or acidic aqueous solutions (for example, aqueous solutions of sodium sulfate or sulfuric acid).
  • the descaling step can also be preceded by mechanical scale-removal treatments (so-called “scale-breaking” treatments), like sand-blasting, shotblasting and abrasive brushing.
  • scale-breaking treatments like sand-blasting, shotblasting and abrasive brushing.
  • the residual scale is removed from the surface of the laminate together with the dechromatized layer beneath.
  • This step is generally carried out by immersing the laminates in acid baths with high oxidizing capability, such as the baths of mixtures of mineral acids (e.g. mixtures of HNO 3 and HF, mixtures of H 2 SO 4 , HCl and H 3 PO 4 , etc.) in the presence of oxidizing compounds, like for example permanganates, persulfates or hydrogen peroxide.
  • acid baths with high oxidizing capability such as the baths of mixtures of mineral acids (e.g. mixtures of HNO 3 and HF, mixtures of H 2 SO 4 , HCl and H 3 PO 4 , etc.) in the presence of oxidizing compounds, like for example permanganates, persulfates or hydrogen peroxide.
  • the protective layer of chromium oxide forms on the surface of the laminate.
  • This step is generally carried out immersing the manufactured product in baths containing nitric acid or mixtures of mineral acids (generally at lower concentrations with respect to the pickling step and with a lower content of the metal ions making up the steel).
  • nitric acid or mixtures of mineral acids generally at lower concentrations with respect to the pickling step and with a lower content of the metal ions making up the steel.
  • the use of pickling baths of nitric acid and hydrofluoric acid leads to the formation of large quantities of nitrogen oxides (NOx) and waste water contaminated by nitrates and fluorinated compounds, which make it necessary to adopt specific measures to keep down gaseous emissions and to purify the waste water.
  • NOx nitrogen oxides
  • the quantity of contaminating compounds to be treated or disposed of depends on the quantity of material removed from the laminate in the baths containing nitric acid and hydrofluoric acid, a quantity that in turn depends - all other conditions being the same - on the duration of the treatment in these baths.
  • the use of pickling baths based on nitric and hydrofluoric acid is currently considered unavoidable for obtaining high quality products.
  • the quantities of material that are removed using these baths are comprised between 60% and 80% of the material removal overall in the pickling process. Consequently, in industrial plants, the lines for the surface treatment of laminates of stainless steel are of dimensions such as to carry out, at the maximum process speed, the pickling and passivation finishing steps with a minimum duration of no less than 60 s for hot rolled laminates and not less than 30 s for cold rolled laminates.
  • the process described in WO 02/12596 comprises an electrolytic pickling step in alternating current carried out in an aqueous solution of sulfuric acid in the presence of Fe 3+ ions or in the presence of at least one second acid selected from hydrofluoric acid and phosphoric acid.
  • the process described in WO 00/15880 comprises an electrolytic pickling step in continuous current carried out in an aqueous solution of sulfuric acid in the presence of ions Fe 3+ ions.
  • the process can also comprise steps of descaling (in baths of molten salts), chemical pickling (in solutions of H 2 SO 4 and HF in the presence of Fe 2+ and Fe 3+ ions) and/or final passivation (in H 2 SO 4 and H 2 O 2 ).
  • EP 2102376 A1 and JP 5222449 describe processes in which the annealing treatment that precedes the pickling is carried out in temperature and oxygen concentration conditions such as to reduce the amount of oxide that forms overall on the laminates.
  • WO 03/052165 describes an electrolytic descaling process (in continuous current) of the laminates made of stainless steel carried out in a bath of sulfuric acid containing ferric ions, ferrous ions and hydrofluoric acid, followed by a chemical pickling treatment in aqueous solutions of sulfuric acid.
  • the duration of the anode treatment in the electrolytic descaling process is correlated to the current density applied and to two parameters that are experimental in nature.
  • EP 1307609 A1 describes an electrolytic pickling process of laminates made of stainless steel carried out in a bath of sulfuric acid with an alternating current of frequency comprised between 40 and 70 Hz and with current density comprised between 10 and 250 A/dm 2 for a duration comprised between 3 s and 60 s.
  • Document WO 02086199 A2 describes an electrolytic descaling process of laminates made of stainless steel carried out with a continuous or alternating current inside an aqueous electrolytic solution of a strong acid (for example hydrochloric acid, sulfuric acid, hydrofluoric acid, etc.), the duration of which is correlated to the current density applied and to two parameters that are experimental in nature.
  • a strong acid for example hydrochloric acid, sulfuric acid, hydrofluoric acid, etc.
  • the main purpose of the present invention is to avoid the drawbacks of the pickling processes of laminates made of stainless steel of the prior art.
  • a purpose of the present invention is to provide a method for pickling a laminate made of stainless steel that makes it possible to obtain a high-quality treated product, but with low environmental impact and lower consumption of raw materials, such as mineral acids and additives.
  • Another purpose of the present invention is to provide a method for pickling a laminate made of stainless steel with improved efficacy, so as to reduce the duration of the pickling treatments and the bulk of the plants necessary to carry it out.
  • laminate made of stainless steel hereafter also “laminate” it is meant a semi-worked product made of stainless steel of the type like a plate, a strip, (a wire, a rod iron, a wire rod, a section bar or similar), of indefinite length.
  • laminate made of stainless steel
  • a semi-worked product made of stainless steel of the type like a plate, a strip, (a wire, a rod iron, a wire rod, a section bar or similar), of indefinite length.
  • the method according to the present invention can be applied to effectively remove the layer of metal oxide (scale) from the surface of the laminate and the dechromatized layer beneath, forming a layer of chrome oxide in its place that protects the laminate from corrosion.
  • the method according to the invention can be used to pickle various types of steel, in particular austenite, martensitic and ferritic steels, whether they are obtained through hot and cold lamination processes (hereafter respectively indicated as “hot rolled laminates” and “cold rolled laminates”).
  • the method according to the invention comprises at least one electrolytic pickling step of the laminate carried out in alternating current (AC) in an aqueous electrolytic solution comprising at least sulfuric acid.
  • AC alternating current
  • the electrolytic pickling in AC is carried out by suitably selecting the frequency of the alternating current applied as a function of the position of the electrodes with respect to the laminate subjected to treatment, as will be illustrated in detail later on.
  • the Applicant has, indeed, found that the efficacy of the electrolytic pickling is greater if, during the crossing path of the electrolytic bath, a given surface portion of the laminate is prevented from being exposed substantially to the same polarization at the pairs of electrodes through which the laminate is made to pass. In this case, indeed, there would be regions of the laminate treated unevenly.
  • the concentration of sulfuric acid in the electrolytic solution is selected in the range 30 g/l - 300 g/l according to the type of steel and the type of treatments to which the laminate has been exposed.
  • the concentration of sulfuric acid is more preferably comprised in the ranged 70-300 g/l.
  • the concentration of sulfuric acid is more preferably comprised in the range 40-200 g/l.
  • the concentration of sulfuric acid is more preferably comprised in the range 30-100 g/l.
  • concentration values of sulfuric acid should be taken as in reference to the concentration of the free acid in the aqueous solution, as measurable, for example, through an acid-base titration or conductometric analysis.
  • the electrolytic solution can also comprise variable concentrations of metal ions in solution deriving from the dissolution of steel, such as Fe, Cr, Ni, Mn, Mo, etc.
  • the total content of metals in solution is typically comprised in the range 0 g/l - 120 g/l.
  • the concentration of dissolved metals depends on the type of steel and on the type of treatments to which the laminate has been subjected. In the case of cold rolled steels, for example, the concentration of dissolved metals is preferably comprised in the range 20-50 g/l. In the case of cold rolled ferritic steels (stabilized and not), the concentration of the dissolved metals is more preferably comprised in the range 30-100 g/l.
  • the concentration of the free acid in the solutions progressively decreases, whereas that of the metal ions, in particular that of the ferrous Fe 2+ ions, increases.
  • the concentration of sulfuric acid can be kept to desired levels through periodic addition of fresh acid or by recycling the aqueous solutions of the acid used in other steps of the method, provided that they have greater concentrations than that desired.
  • the electrolytic pickling is carried out keeping the electrolytic solution at a temperature comprised in the range 30-100°C.
  • the temperature is more preferably comprised in the range 40-95°C, whereas for cold rolled, the temperature is more preferably comprised in the range 30-95°C.
  • the temperature is preferably comprised in the range 40-70°C for steels of the austenitic type, in the range 30-50°C for stabilized ferritic steels and in the range 30-45°C for unstabilized ferritic steels.
  • the alternating current (AC) used in the electrolytic pickling has a density (referring to the unit surface of the laminate) comprised in the range 5-60 A/dm 2 .
  • the current density is preferably comprised in the range 15-60 A/dm 2 , even more preferably in the range 20-50 A/dm 2 .
  • the current density can preferably be selected as a function of the type of steels, for example, as follows:
  • the frequency of the AC current is comprised in the range 5-150 Hz.
  • the frequency is kept at a constant value during the treatment.
  • it can also be varied as a function of the process requirements, for example to increase the quality of the treatment or to control the pickling speed as a function of the feeding speed of the laminate to the pickling plant.
  • the electrolytic pickling has a duration comprised between 3 and 40 seconds, both for hot rolled laminates and for cold rolled laminates.
  • the duration of the electrolytic pickling is preferably comprised in the range 8-60 seconds, even more preferably in the range 10-50 seconds; in the case of hot rolled austenite steels, the duration is preferably comprised in the range 10-20 seconds.
  • the duration of the electrolytic pickling in AC current can preferably be selected as a function of the type of steels, for example, as follows:
  • the method according to the invention also comprises a finishing and final passivation step (hereafter also just “finishing”).
  • This step which is generally carried out after having subjected the laminate to careful washing with water to eliminate the residues of sulfuric acid and iron oxides possibly still present on its surface, has the purpose of oxidising the surface of the laminate so as to form a protective layer of chromium oxide.
  • the finishing step can be carried out according to the prior art.
  • the finishing step is carried out by placing the surface of the laminate in contact with an aqueous solution of at least one mineral acid having an oxidation-reduction chemical potential (measured with respect to a reference electrode Ag/AgCl) comprised between 100 and 800 mV, preferably between 200 mV and 600 mV (finishing solution).
  • an oxidation-reduction potential can be obtained, for example, with aqueous solutions comprising one or more acids selected from nitric acid, or sulfuric acid and Fe 3+ ions possibly in the presence of free hydrofluoric acid.
  • the concentration of Fe 3+ ions in the finishing solution varies in the range 5-50 g/l.
  • the mixture of acids to be used in the finishing solution is concerned, it is selected as a function of the type of steel of the laminate.
  • the mixture of mineral acids used in the finishing step is a mixture of nitric acid and hydrofluoric acid (nitric-hydrofluoric finishing).
  • the concentration of nitric acid in the finishing solution is preferably comprised in the range 50-150 g/l, whereas that of the free hydrofluoric acid is preferably comprised in the range 5-45 g/l.
  • the concentration of nitric acid is more preferably comprised in the range 100-150 g/l, whereas that of free hydrofluoric acid is preferably comprised in the range 20-35 g/l.
  • the concentration of nitric acid is more preferably comprised in the range 75-130 g/l, whereas that of free hydrofluoric acid is preferably comprised in the range 5-20 g/l.
  • the concentration of Fe 3+ ions in the finishing solution is preferably comprised in the range 5-35 g/l.
  • the concentration of nitric acid is more preferably comprised in the range 60-150 g/l, whereas that of hydrofluoric acid is preferably comprised in the range 10-30 g/l.
  • the concentration of nitric acid is more preferably comprised in the range 50-130 g/l, whereas that of hydrofluoric acid is preferably comprised in the range 10-25 g/l.
  • the mixture of mineral acids used in the finishing step is an aqueous solution of sulfuric acid containing, possibly, also free hydrofluoric acid (sulphuric or sulphuric-hydrofluoric finishing) comprising Fe 3+ and Fe 2+ ions.
  • the concentration of sulfuric acid in the finishing solution is preferably comprised in the range 20-150 g/l, whereas that of the possible free hydrofluoric acid is preferably comprised in the range 5-30 g/l.
  • the concentration of Fe 3+ ions is preferably comprised in the range 5-80 g/l, whereas the concentration of Fe 2+ ions is preferably comprised in the range 5-20 g/l.
  • the concentration of sulfuric acid is more preferably comprised in the range 60-150 g/l, whereas that of the possible free hydrofluoric acid is preferably comprised in the range 10-30 g/l.
  • the concentration of sulfuric acid is more preferably comprised in the range 40-100 g/l, whereas that of the possible free hydrofluoric acid is preferably comprised in the range 5-25 g/l.
  • the concentration of sulfuric acid is more preferably comprised in the range 40-150 g/l, whereas that of the possible free hydrofluoric acid is preferably comprised in the range 5-30 g/l.
  • the concentration of sulfuric acid is more preferably comprised in the range 30-150 g/l, whereas that of the possible free hydrofluoric acid is preferably comprised in the range 5-25 g/l.
  • the concentration of Fe 3+ ions is more preferably comprised in the range 45-90 g/l, whereas the concentration of Fe 2+ ions is more preferably comprised in the range 5-40 g/l.
  • the concentration of Fe 3+ ions is more preferably comprised in the range 35-80 g/l, whereas the concentration of Fe 2+ ions is more preferably comprised in the range 5-40 g/l.
  • the concentration of Fe 3+ ions is preferably comprised in the range 25-80 g/l, whereas the concentration of Fe 2+ ions is preferably comprised in the range 5-20 g/l.
  • the concentration of Fe 3+ ions is preferably comprised in the range 20-70 g/l, whereas the concentration of Fe 2+ ions is preferably comprised in the range 5-25 g/l.
  • the finishing solution comprises an aqueous solution of nitric acid, as single acid, also comprising Fe 3+ ions.
  • concentration of nitric acid in the finishing solution is preferably comprised in the range 20-100 g/l, whereas that of the Fe 3+ ions is on the other hand comprised in the range 20-50 g/l. This finishing solution is particularly preferred in the case of ferritic cold rolled laminates.
  • a further preferred finishing solution comprises nitric acid in a concentration comprised in the range 40-100 g/l and dissolved metals in a concentration comprised in the range 0-10 g/l (substantially in the absence of Fe 3+ ions).
  • finishing solutions that are particularly preferred are those that do not comprise nitric acid, since they allow the environmental impact of the process to be reduced in terms of emissions of polluting gases (NOx) and nitrate and fluorinated compounds in the waste water.
  • NOx polluting gases
  • the finishing solution is kept at a temperature that can vary from 25°C to 65°C.
  • the duration of the finishing treatment varies from 10 seconds to 60 seconds.
  • the finishing step of the pickled laminate can be carried out by placing the laminate in contact with one or more of the aforementioned finishing solutions as a function of the type of steel, of the lamination process undergone and of the previous pickling steps.
  • the finishing step can comprise a first treatment with a sulphuric-hydrofluoric solution followed by a second treatment with a nitric-hydrofluoric solution.
  • This embodiment of the finishing step is particularly suitable in the case of cold rolled laminates.
  • the composition of the scale depends strictly on the type of lamination undergone - hot or cold - and on possible annealing heat treatments to which the laminate has been subjected.
  • the method according to the invention can comprise one or more further treatment steps.
  • the treatment method can advantageously also comprise a chemical descaling step to promote the removal of scale in the subsequent electrolytic pickling step.
  • the chemical descaling step is carried out by placing the laminate in contact with an aqueous solution comprising sulfuric acid and possibly metal ions (descaling solution).
  • the concentration of sulfuric acid in the descaling solution is selected in the range 150 g/l - 300 g/l, preferably in the range 200 g/l - 250 g/l, according to the type of steel and the type of treatments to which the laminate has been subjected.
  • the concentration of dissolved metals is typically comprised in the range 0-120 g/l.
  • the descaling solution comprises 200-280 g/l of sulfuric acid and 30-50 g/l of dissolved metals.
  • the duration of the chemical descaling treatment is typically comprised in the range 15-60 seconds, preferably 25-50 seconds.
  • the temperature of the descaling solution is preferably kept in the range 70-98°C.
  • the chemical descaling step although possible, is generally omitted, since it is unnecessary.
  • the quality of the pickled surfaces can be improved by also subjecting the laminate to at least one electrolytic treatment in continuous current (DC), using an electrolytic solution having the same composition as the solution used in the treatment in AC current or similar composition.
  • DC continuous current
  • the electrolytic treatment in DC current is carried out by applying a DC current of density comprised in the range 4-14 A/dm 2 .
  • the current density DC is preferably comprised in the range 5-12 A/dm 2 .
  • the duration of the treatment in DC current is comprised between 3 and 35 seconds, such a duration referring to the period in which a given surface portion of the laminate is anodically polarized.
  • the duration of the electrolytic pickling in DC current can vary as a function of the type of steels in the following way:
  • the treatment in DC current can be carried out before or after the treatment in AC current, preferably before.
  • the treatment stages in AC and DC current can be carried out in the same tank or in separate tanks, arranged in series in the pickling plant.
  • the ratio between the duration of the treatment in AC current and the duration of the anodic polarization obtained with the DC treatment is generally comprised between 0.15 and 1, preferably between 0.20 and 0.50.
  • the concentration of sulfuric acid and that of dissolved metals varies over time as the treatment of the laminates proceeds. Also in these cases, the concentrations of the different species can be restored through the discharge of the spent solutions, the addition (periodic or in continuous) of fresh reactants, water and for the metals through the addition of oxidants such as hydrogen peroxide, organic and/or inorganic peracids and/or their salts.
  • the method of the invention can also comprise the conventional steps (intermediate or preliminary) of washing and degreasing the surface of the laminate with suitable aqueous solutions containing surfactants or other additives.
  • the washing steps (which can be carried out by immersion, spraying with water jets and possibly with the help of metallic brushes) have the purpose of eliminating the residues of the previous treatments from the surface and avoiding contamination of the solutions used in the subsequent steps of the method.
  • the electrolytic pickling step in particular, can be carried out in a tank of the type described in patent application WO 2011/039596 .
  • Figure 1 schematically represents a possible embodiment of an apparatus in which it is possible to carry out the electrolytic pickling step according to the method of the invention.
  • the apparatus wholly indicated with 10, comprises a treatment tank 12 suitable for containing the electrolytic solution SE and inside which the laminate 11 is made to pass in continuous along a direction and in the advancing sense indicated by the arrow F.
  • the position of the laminate inside the treatment tank 12 is determined by the rollers 20 and 21 and by the pull applied on the strip.
  • the apparatus 10 also comprises at least two pairs of electrodes 14 that are opposite one another and between which the laminate 11 is made to pass in continuous.
  • Each pair of electrodes 14 comprises at least one first electrode 15 facing one of the two faces of the laminate 11 and at least one second electrode 17 facing the other of the two faces of the laminate 11.
  • the electrodes 15, 17, are also substantially equidistant from the laminate 11, each of them being at a distance Lc from the laminate in general comprised between 50 and 250 mm.
  • the electrodes 15, 17 are arranged in a direction substantially parallel to the faces of the laminate along the path in the tank 12 and they extend substantially for the entire width La of the laminate (the width La is not shown in the figures).
  • the two electrodes 15, 17 of a pair of electrodes 14 are separated by a distance Lg preferably comprised between 100 and 500 mm.
  • Each of the electrodes 15, 17 has a length Le, measured along the movement direction of the laminate, preferably comprised between 300 mm and 2200 mm.
  • Each pair of electrodes 14 is a distance Lx from the next pair, in the movement direction of the laminate, in general comprised between 100 and 800 mm.
  • the electrodes 15, 17 of each pair of electrodes 14 are immersed in the electrolytic solution SE and can be associated with an electric power supply group (not shown in the figures) capable of delivering a continuous current DC or an alternating current AC at variable frequency.
  • an electric power supply group capable of delivering a continuous current DC or an alternating current AC at variable frequency.
  • a first preferred configuration is that for which the AC current is supplied to the electrodes 15, 17 so that the two electrodes of each pair 14 are with voltage in phase between them, so as to have, at a given moment, on both of the electrodes, a polarization of the same sign.
  • the electrodes 15 and 17 it is possible to connect the electrodes 15 and 17 to a phase of a transformer or of an inverter taking care to arrange a sufficient distance between pairs of electrodes 14 connected to different phases.
  • there is at least one separator element made of an insulating material for example in the form of an immersing roller coated in plastic material or of a static separator made from plastic material (not shown in the figures).
  • the separators made from insulating material allow the formation of dispersed currents between electrodes of adjacent pairs that have opposite polarization to be reduced.
  • a second preferred configuration provides that the electrodes 15 and 17 facing each other are connected to two different phases of the alternating current; in this case it is preferable for successive pairs of electrodes 14, if adjacent and not separated by immersing rollers and other insulating separators, to be connected to the same phases; pairs of electrodes separated by appropriate distance and by immersing rollers and insulating separators, on the other hand, will be connected to different phases so as to minimise the dispersed currents and, at the same time, avoid unbalanced loads on the power supply network.
  • the resulting electric field has current lines that are substantially vertical and orthogonal to the surface of the laminate, which is thus passed through by the current along the thickness.
  • the electrolytic pickling treatment is carried out by applying to the electrodes 15, 17 an alternating current of frequency f, variable from 5 Hz to 150 Hz, said frequency f being correlated to the forward speed v (expressed in m/s) of the laminate and to the length L e (expressed in metres) of the electrodes 15, 17 by the relation (1) F Hz ⁇ A ⁇ v / L e where A is a rational number greater than 1, preferably greater than 2. Generally, A does not exceed the value 300.
  • the solution indicated above to improve the efficiency of treatment of the laminate can also be applied to the case in which the apparatus for carrying out the electrolytic treatment comprises electrodes consisting of a plurality of elements (for example plates of the type described in WO 2011/039596 ).
  • This configuration schematically illustrated in figure 2 , has the advantage of avoiding the accumulation of electrolysis gases and of solid residues (essentially metal oxides) that detach from the surface during the electrolytic process, thus improving the efficiency of the treatment.
  • the apparatus of figure 2 comprises pairs of electrodes 140 consisting of two groups 150, 170 of elements 160, 180.
  • the elements 160, 180 extend for the entire width of the laminate and have a length L b (measured in the forward direction of the laminate).
  • the elements 160, 180 are arranged substantially parallel with respect to the laminate 11.
  • the distance between two adjacent elements 160, 180 is indicated in figure 2 with reference L d .
  • Each element 160, 180, in the apparatus 10 performs the function of electrode in the same way as the electrodes 17, 15 of the apparatus 10 described in figure 1 .
  • figure 2 the elements indicated with the same reference symbols used for figure 1 correspond to the same elements described for figure 1 .
  • the electrolytic treatment of the laminate 11 could not be uniform over the entire surface for particular geometric arrangements of the electrodes 150, 170, of the elements 160, 180 and of the laminate 11.
  • non-uniform treatments can be encountered when the distance L d between two adjacent elements is close to or greater than the distance L c between the element 160, 180 and the laminate 11.
  • this drawback can be overcome in the case of an apparatus of the type illustrated in figure 2 by applying to the electrodes an alternating current of frequency f, comprised in the range 5 Hz - 150 Hz, said frequency f being correlated to the forward speed v (expressed in m/s) of the laminate and to the length L b (expressed in metres) of the element 160, 180 by the relation (2) F Hz ⁇ A ′ ⁇ v / L b where A' is a rational number greater than 1, preferably comprised between 1 and 25, more preferably comprised between 1 and 10.
  • the frequency f when the ratio between the distance Lg between the opposite electrodes 150, 170 and the distance L d of the elements 160, 180 that form said opposite electrodes 150, 170 is greater than 4, it is preferable for the frequency f to respect at least the relation (1).
  • the aforementioned ratio L g /L d is equal to or less than 4, it is preferable for the frequency f to respect at least the relation (2).
  • the method according to the present invention makes it possible to overcome or at least lessen the drawbacks highlighted by the state of the art in the field of pickling treatments of laminates made of stainless steel.
  • the pickling treatments carried out with the method according to the invention have an improved efficacy, making it possible to obtain high-quality pickled surfaces with an overall duration of the treatment that is short.
  • the method according to the invention also contemplating carrying out a final finishing and passivation step of the laminates in mixtures containing nitric and hydrofluoric acid, determines a reduction in the environmental impact with respect to that typically observed in the processes of the prior art.
  • the pickling carried out according to the present invention indeed, is able to remove - in certain cases - up to 80% by weight of the overall mass of scale and dechromatized steel, thus making it sufficient to have a finishing step in nitric-hydrofluoric acid that is even very short and, consequently, significantly limiting the formation of polluting residues to be disposed of (nitrate, fluorinated compounds and emissions of NOx).
  • the improved efficacy of the treatment method according to the present invention makes it possible to treat the laminates in plants of smaller dimensions with respect to the state of the art, being able to provide for shorter residency times of the laminate in contact with the pickling baths.
  • a further advantage of the method according to the present invention is the fact that, since at least one electrolytic pickling step is provided, it is possible to adjust the overall speed of the pickling process by acting on the current intensity applied in this step. In the case of slowing down of the pickling line, for example, it is possible to temporarily attenuate the pickling action of the sulfuric acid (decreasing the intensity of the current applied), thus avoiding phenomena of excessive dissolving erosion of the laminate.
  • the method according to the present invention was applied to treat strips of stainless steel of different chemical composition, obtained through hot or cold rolling processes, possibly accompanied by annealing treatments.
  • the production and treatment plant comprised the following sections:
  • AISI 304 (L1), AISI 430 (L2), AISI 441 (L3), AISI 409 (L4)).
  • the concentrations of the different species in the aqueous solutions and the operative conditions adopted in each step of the process together with the dimensional parameters of the laminates L1-L4 are given in Table 3.
  • the efficacy of the method was evaluated by calculating the percentage amount of metal removed from the laminate and/or dissolved during each step with respect to the amount of metal removed and/or dissolved overall.
  • the method according to the invention applied to the hot rolled laminates, has resulted in a significant reduction of the polluting substances to be treated.
  • the production and treatment plant comprised the following sections:
  • the same pickling treatment was applied to a fifth laminate (AISI 304 (L9)) obtained through a hot rolling and annealing process.
  • the efficacy of the method was evaluated by calculating the percentage amount of metal removed from the laminate and/or dissolved during each step with respect to the amount of metal removed and/or dissolved overall.
  • the finishing treatments carried out in the conditions given in Table 4 proved sufficient to obtain a uniformly passivated surface.
  • Such a treatment generated a significantly small amount of polluting products to be disposed of (muds containing nitrate, fluorinated compounds and emissions of NO x ), since the amount of metal removed and/or dissolved in the finishing step is reduced to values of 20% by weight (L9) of the mass of steel removed and/or dissolved overall in the entire treatment.
  • L9 20% by weight
  • the amount of metal removed and/or dissolved in the nitric and/or hydrofluoric acid baths can reach 80% by weight of the amount pickled overall.

Landscapes

  • 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)
  • ing And Chemical Polishing (AREA)
  • Chemical Treatment Of Metals (AREA)

Claims (13)

  1. Procédé de traitement en continu de la surface d'un stratifié en acier inoxydable comprenant au moins les étapes suivantes :
    (a) faire passer ledit stratifié (11) en continu dans un réservoir (12) contenant une solution électrolytique aqueuse (SE) d'acide sulfurique, ledit stratifié (11) passant entre au moins deux électrodes (150, 170) immergées dans ladite solution électrolytique (SE) et disposées dans une direction substantiellement parallèle à la direction de déplacement du stratifié (11) et ayant une longueur Le mesurée le long de ladite direction, lesdites électrodes (150, 170) étant situées devant les faces opposées dudit stratifié (11) et étant placées dans une position dans laquelle elles se font face,
    (b) soumettre ledit stratifié (11) à un traitement de décapage électrolytique en appliquant un courant alternatif ayant une fréquence f comprise entre 5 Hz et 150 Hz, ladite fréquence f étant corrélée à ladite vitesse avant v du stratifié (11) et à ladite longueur Le desdites électrodes (150, 170) par la relation F ≥ (A·v)/ Le, où A est un nombre rationnel supérieur à 1, de préférence supérieur à 2 ;
    (c) soumettre ledit stratifié décapé de façon électrolytique (11) à un traitement de finition de surface et à un traitement de passivation de surface.
  2. Procédé selon la précédente revendication, dans lequel ladite étape (a) est exécutée en faisant passer ledit stratifié (11) en continu entre au moins deux électrodes (150, 170), chacune desdites électrodes (150, 170) comprenant une pluralité d'éléments (160, 180) disposés côte à côte de manière substantiellement parallèle et disposés transversalement à la direction de déplacement du stratifié (11), chacun desdits éléments (160, 180) ayant une longueur Lb mesurée le long de ladite direction de déplacement du stratifié (11), lesdites électrodes (150, 170) étant situées devant les faces opposées dudit stratifié (11) et étant placées dans une position dans laquelle elles se font face, et en appliquant un courant alternatif ayant une fréquence f comprise entre 5 Hz et 150 Hz, ladite fréquence f étant corrélée à ladite vitesse v et à ladite longueur Lb par la relation f ≥ (A'·v)/ Lb, où A' est un nombre rationnel supérieur à 1, de préférence compris entre 1 et 25, mieux encore compris entre 1 et 10.
  3. Procédé selon la revendication 1 ou 2, dans lequel l'acide sulfurique est présent dans ladite solution électrolytique aqueuse en une concentration comprise dans la plage de 40 à 300 g/l.
  4. Procédé selon l'une ou plusieurs des revendications précédentes, dans lequel, avant ladite étape (a), ledit stratifié (11) est soumis à une étape de détartrage chimique (a') dans une solution aqueuse d'acide sulfurique en une concentration comprise dans la plage de 150 à 300 g/l (solution de détartrage), ladite solution de détartrage comprenant en option des ions métalliques en une concentration comprise dans la plage de 0 à 120 g/l.
  5. Procédé selon l'une ou plusieurs des revendications précédentes, dans lequel ledit décapage électrolytique comprend au moins une première phase et une deuxième phase, ladite première phase étant réalisée en courant continu avec polarisation anodique dudit stratifié (11) et ladite deuxième phase étant réalisée en courant alternatif.
  6. Procédé selon la revendication 5, dans lequel le rapport entre la durée du traitement en courant alternatif et la durée de la polarisation anodique dudit stratifié (11) dans le traitement en courant continu est compris entre 0,15 et 1, de préférence entre 0,20 et 0,50.
  7. Procédé selon l'une ou plusieurs des revendications précédentes, dans lequel ledit décapage électrolytique en courant alternatif est réalisé en appliquant un courant alternatif ayant une fréquence f comprise entre 5 Hz et 150 Hz, la densité de courant étant comprise entre 5 A/dm2 et 60 A/dm2, la durée du traitement étant comprise entre 3 et 40 s.
  8. Procédé selon la revendication 5, dans lequel ledit décapage électrolytique en courant continu est réalisé en appliquant un courant continu avec une densité de polarisation anodique de la bande comprise entre 4 A/dm2 et 14 A/dm2, la durée de ladite polarisation anodique de la bande étant comprise entre 3 s et 20 s.
  9. Procédé selon l'une ou plusieurs des revendications précédentes, dans lequel ladite étape (c) est exécutée en mettant ledit stratifié en contact avec une solution aqueuse (solution de finition et de passivation) ayant un potentiel chimique d'oxydoréduction (mesuré par rapport à une électrode de référence du type Ag/AgCl) compris entre 200 et 800 mV, de préférence entre 200 mV et 400 mV.
  10. Procédé selon l'une ou plusieurs des revendications précédentes, dans lequel ladite étape (c) comprend une première sous-étape de traitement avec une première solution de finition et de passivation et une deuxième sous-étape de traitement avec une deuxième solution de finition et de passivation ayant une composition différente de ladite première solution.
  11. Procédé selon l'une ou plusieurs des revendications précédentes, dans lequel ladite solution de finition et de passivation est une solution aqueuse d'acide nitrique comprenant des ions Fe3+ et éventuellement de l'acide fluorhydrique.
  12. Procédé selon l'une ou plusieurs des revendications 1 à 10, dans lequel ladite solution de finition et de passivation est une solution aqueuse d'acide sulfurique et d'acide fluorhydrique comprenant des ions Fe3+ et des ions Fe2+.
  13. Procédé selon l'une ou plusieurs des revendications précédentes, dans lequel on fait passer ledit stratifié (11) dans ledit réservoir (12) entre au moins une première et une deuxième paire (140) d'électrodes (150, 170) immergées dans ladite solution électrolytique (SE) et disposées dans une direction substantiellement parallèle à la direction de déplacement du stratifié (11), un élément de séparation étant intercalé entre lesdites paires d'électrodes (140), lequel est fait d'un matériau isolant, et se présentant sous la forme d'un rouleau d'immersion ou d'un séparateur statique, approprié pour réduire la formation de courants dispersés entre des électrodes adjacentes ayant une polarisation contraire.
EP14722742.5A 2013-03-29 2014-03-27 Procédé de traitement en continu de la surface d'un stratifié en acier inoxydable dans une solution à base d'acide sulfurique Active EP2978879B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT000493A ITMI20130493A1 (it) 2013-03-29 2013-03-29 Metodo per trattare in continuo la superficie di un laminato di acciaio inossidabile in una soluzione a base di acido solforico
PCT/IB2014/060230 WO2014155341A1 (fr) 2013-03-29 2014-03-27 Procédé de traitement en continu de la surface d'un stratifié en acier inoxydable dans une solution à base d'acide sulfurique

Publications (2)

Publication Number Publication Date
EP2978879A1 EP2978879A1 (fr) 2016-02-03
EP2978879B1 true EP2978879B1 (fr) 2017-11-08

Family

ID=48444515

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14722742.5A Active EP2978879B1 (fr) 2013-03-29 2014-03-27 Procédé de traitement en continu de la surface d'un stratifié en acier inoxydable dans une solution à base d'acide sulfurique

Country Status (5)

Country Link
EP (1) EP2978879B1 (fr)
CN (1) CN105143523B (fr)
BR (1) BR112015020701B1 (fr)
IT (1) ITMI20130493A1 (fr)
WO (1) WO2014155341A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105040088A (zh) * 2015-08-11 2015-11-11 佛山市环宇新型材料有限公司 一种带钢电解除污装置
CN107653485A (zh) * 2017-10-11 2018-02-02 徐州中泰能源科技有限公司 一种绿色环保的铁制品除锈方法
BE1026907B1 (nl) * 2018-12-20 2020-07-22 Aperam Stainless Belgium Werkwijze voor het produceren van op ten minste drie verschillende manieren afgewerkt roestvast plaatstaal
BE1026906B1 (nl) * 2018-12-20 2020-07-22 Aperam Stainless Belgium Werkwijze voor het produceren van op ten minste drie verschillende manieren afgewerkt roestvast plaatstaal
KR102286367B1 (ko) * 2019-11-11 2021-08-05 주식회사 포스코 고분자 연료전지 분리판용 스테인리스강의 제조방법
KR102497442B1 (ko) * 2020-11-25 2023-02-08 주식회사 포스코 접촉저항이 향상된 고분자 연료전지 분리판용 오스테나이트계 스테인리스강 및 그 제조 방법
CN113337875B (zh) * 2021-04-02 2023-03-28 无锡透平叶片有限公司 一种铁基变形高温合金锻件低倍流线腐蚀液及其腐蚀方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8517606D0 (en) * 1985-07-12 1985-08-21 Bekaert Sa Nv Cleaning by electrochemical pickling
IT1302202B1 (it) 1998-09-11 2000-07-31 Henkel Kgaa Processo di decapaggio elettrolitico con soluzioni esenti da acidonitrico.
IT1317896B1 (it) 2000-08-10 2003-07-15 Ct Sviluppo Materiali Spa Metodo di decapaggio elettrolitico continuo di prodotti metallici concelle alimentate a corrente alternata.
ES2232564T3 (es) * 2000-12-18 2005-06-01 Centro Sviluppo Materiali S.P.A. Decapado y desincrustado electrolitico continuo de acero al carbono y de acero inoxidable.
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.
ITRM20010747A1 (it) 2001-12-19 2003-06-19 Ct Sviluppo Materiali Spa Procedimento a ridotto impatto ambientale e relativo impianto per descagliare, decapare e finire/passivare, in modo continuo, integrato e fl
ITMI20062187A1 (it) 2006-11-14 2008-05-15 Sviluppo Materiali Spa Processo di ricottura e decapaggio
DE102008057151A1 (de) * 2008-11-13 2010-05-27 Henkel Ag & Co. Kgaa Verfahren zum Herstellen eines elektrolytisch verzinkten hochfesten Stahlbleches
JP5222449B2 (ja) 2008-12-26 2013-06-26 三菱伸銅株式会社 めっき付銅条材のスリット方法及びめっき付銅条材のスリット装置
IT1395853B1 (it) 2009-09-30 2012-10-26 Tenova Spa Gruppo di preparazione superficiale per linee di produzione di nastri metallici

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
BR112015020701B1 (pt) 2021-08-24
CN105143523A (zh) 2015-12-09
CN105143523B (zh) 2018-06-19
EP2978879A1 (fr) 2016-02-03
ITMI20130493A1 (it) 2014-09-30
WO2014155341A1 (fr) 2014-10-02
BR112015020701A2 (pt) 2017-07-18

Similar Documents

Publication Publication Date Title
EP2978879B1 (fr) Procédé de traitement en continu de la surface d'un stratifié en acier inoxydable dans une solution à base d'acide sulfurique
US7799199B2 (en) Process and plant for descaling, pickling and finishing passivating stainless steel strips, and strips so obtainable
KR101289147B1 (ko) 표면품질이 우수한 저크롬 페라이트계 스테인리스 냉연강판을 제조하기 위한 친환경 고속 산세 프로세스
FI101981B (fi) Menetelmä ruostumattoman teräksen peittaukseen ja passivointiin ilman typpihappoa
EP2761063B1 (fr) Décapage d'acier inoxydable dans un bain acide électrolytique, oxydant
KR100650961B1 (ko) 무질산 용액을 사용한 전해 산세척 방법
US20040031696A1 (en) Continous electrolytic pickling method for metallic products using alternate current supplied cells
AU708994B2 (en) Annealing and descaling method for stainless steel
KR100696850B1 (ko) 저크롬 페라이트계 스테인레스강의 고속산세방법
JPH09137300A (ja) ステンレス鋼からなる帯板製品を製造するための方法及び設備
KR101359098B1 (ko) 오스테나이트계 스테인리스 냉연강판을 제조하기 위한 고속 산세 프로세스
JP6031606B2 (ja) オーステナイト系ステンレス冷延鋼板を製造するための高速酸洗プロセス
EP2978878B1 (fr) Procédé de traitement continu de la surface d'un stratifié fait d'acier inoxydable dans une solution à base d'acide chlorhydrique
JP3792335B2 (ja) ステンレス鋼帯の脱スケールにおける仕上げ電解酸洗方法
KR101382934B1 (ko) 내식성 향상을 위한 오스테나이트계 스테인리스 냉연강판의 고속 산세 프로세스
KR102300834B1 (ko) 스테인리스강 산세용 이온성 액체 및 이를 이용한 스테인리스강의 산세방법
Covino et al. Pickling of Stainless Steels--a Review
KR101353856B1 (ko) 오스테나이트계 스테인리스 냉연강판을 제조하기 위한 저온 고속 산세 프로세스
JP2517353B2 (ja) ステンレス鋼帯の脱スケ―ル方法
KR101242990B1 (ko) 표면 품질 개선을 위한 페라이트계 스테인리스 냉연강판의 산세공정
JPH10110299A (ja) 鋼帯の電解脱スケール方法
JPH09296285A (ja) オーステナイト系ステンレス熱延鋼帯の酸洗方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20150819

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20170530

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 944242

Country of ref document: AT

Kind code of ref document: T

Effective date: 20171115

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602014016877

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180208

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180208

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180308

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180209

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602014016877

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20180809

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20180327

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180327

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180327

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180331

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180327

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180327

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171108

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20140327

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

REG Reference to a national code

Ref country code: AT

Ref legal event code: UEP

Ref document number: 944242

Country of ref document: AT

Kind code of ref document: T

Effective date: 20171108

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230508

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20240326

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20240304

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FI

Payment date: 20240325

Year of fee payment: 11

Ref country code: DE

Payment date: 20240327

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20240327

Year of fee payment: 11

Ref country code: IT

Payment date: 20240321

Year of fee payment: 11

Ref country code: FR

Payment date: 20240325

Year of fee payment: 11

Ref country code: BE

Payment date: 20240327

Year of fee payment: 11