EP2660364B1 - Procédé de décapage rapide, écologique, de production de tôle d'acier inoxydable à base de ferrite et à faible teneur en chrome, laminée à froid doté de qualité de surface supérieure - Google Patents

Procédé de décapage rapide, écologique, de production de tôle d'acier inoxydable à base de ferrite et à faible teneur en chrome, laminée à froid doté de qualité de surface supérieure Download PDF

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EP2660364B1
EP2660364B1 EP11852757.1A EP11852757A EP2660364B1 EP 2660364 B1 EP2660364 B1 EP 2660364B1 EP 11852757 A EP11852757 A EP 11852757A EP 2660364 B1 EP2660364 B1 EP 2660364B1
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Prior art keywords
steel sheet
sulfuric acid
electrolyte
stainless steel
pickling
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German (de)
English (en)
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EP2660364A4 (fr
EP2660364A2 (fr
Inventor
Ji-Hun Kim
Dong-Hoon Kim
Jin-Suk Kim
Sang-Kyo CHOI
Yong-Heon Lee
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Posco Holdings Inc
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Posco Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/086—Iron or steel solutions containing HF
    • C—CHEMISTRY; METALLURGY
    • 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
    • C25F1/12—Pickling; Descaling in melts
    • C25F1/14—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 relates to a high-speed steel sheet pickling process for producing a ferrite-based cold-rolled stainless steel sheet having superior surface qualities, and more particularly, to a pickling process not using nitric acid.
  • stainless steel sheets After cold rolling, stainless steel sheets are heat-treated at a temperature of 800°C to 1150°C to obtain desired mechanical properties.
  • oxide scale e.g., SiO 2 and (Cr,Fe) 3 O 4 .
  • oxide scale spoils the appearance of steel sheets and reduces the quality of steel sheets.
  • oxide scale reduces the corrosion resistance of steel sheets because steel sheets may start to corrode from the presence of oxide scale.
  • oxide scale is removed by various methods such as: physical descaling including brushing or shot ball blasting; electrolytic descaling using a sodium sulfate electrolyte, a sulfuric acid electrolyte, or a nitric acid electrolyte; and chemical descaling using a salt bath or an acid mixture.
  • physical descaling including brushing or shot ball blasting
  • chemical descaling using a salt bath or an acid mixture is known as a pickling process.
  • Stainless steel is treated through a pickling process to improve surface appearance and quality and to evenly form a corrosion-resistant passive film thereon
  • pickling methods for descaling stainless steel include: a nitric acid electrolytic method in which current is applied to a nitric acid solution while passing a steel sheet therethrough; and a chemical descaling method using a mixture of a nitric acid (80 g/l to 180 g/l) and a hydrofluoric acid (2 g/l to 40 g/l).
  • Nitric acid reduces the pH level of a pickling bath to increase the activity of hydrofluoric acid, and oxidizes Fe2+ ions into Fe3+ ions to maintain the oxidation-reduction potential at a level suitable for pickling.
  • nitric acid as a pickling solution results in emission of NOx, a regulated air pollutant, and nitric nitrogen (NO 3 -N) in waste acids and washing water. Therefore, it is necessary to add and operate pollution prevention equipment for a pickling process so as to satisfy tightened domestic and foreign environmental regulations limiting the total amount of nitrogen in effluent and the concentration of NOx emitted from air pollutant emission facilities.
  • installation and operating costs of such equipment markedly increase unit cost of production.
  • German Patent No. 3937438 discloses a technique of using a pickling solution including sulfuric acid, hydrofluoric acid, and iron sulfate, and adding hydrogen peroxide to the pickling solution to maintain the oxidation-reduction potential of the pickling solution equal to or greater than 300 mV.
  • techniques have been constantly proposed since the 1990s, mainly concerned with regulating appropriate amounts of hydrofluoric acid, iron ions, air, and hydrogen peroxide, or appropriate oxidation-reduction potentials (ORP) in solutions, as in US Patent No. 5154774 and European Patent No. 236354 .
  • ORP oxidation-reduction potentials
  • the majority of such techniques are used for producing limited kinds of products such as wire rods, steel rods, and steel plates which have easy to meet quality requirements.
  • US Patent No. 5908511 discloses a technique for performing a pickling process using a pickling solution including: sulfuric acid, hydrofluoric acid, ferric salt, periodically added hydrogen peroxide, a wetting agent, a polishing agent, and a corrosion inhibitor while controlling concentrations of the wetting agent, the polishing agent, and the corrosion inhibitor and automatically managing the pickling solution based on the amount of Fe(III) and ORP related to the amount of Fe(III).
  • the pickling solution was commercialized as CLEANOX352, and has become the most widely used product in the art to which the present invention pertains. This technique is practically used for producing wire rods and hot-rolled products, but increases unit cost in production by 20% or more and requires a complicated solution and control method. Furthermore, the technique has a slow pickling weight reduction rate of about 1.5 g/m 2 -min to about 3 g/m 2 -min, and thus, is not suitable for a high-speed pickling process that has to be performed within 10 seconds to 100 seconds.
  • aspects of the present invention provide a pickling process for rapidly producing a low-chrome ferrite-based cold-rolled stainless steel sheets having high quality by using an electrolyte solution not including nitric acid, and a pickling process for rapidly removing Si oxide by using a mixed acid solution.
  • An open circuit potential of the cold-rolled stainless steel sheet immersed in the mixed acid solution may be maintained within a range of -0.2 V to 0.2 V, and the cold-rolled stainless steel sheet may be immersed in the mixed acid solution for 10 seconds to 100 seconds.
  • the process may further include performing a neutral salt electrolyte treatment to remove Cr-rich scale from the steel sheet using a neutral salt electrolyte solution comprising a sodium sulfate electrolyte.
  • the neutral salt electrolyte treatment may be performed by immersing the steel sheet in the neutral salt electrolyte solution maintained at 50°C to 90°C and applying a current of 10 A/dm 2 to 30 A/dm 2 to the steel sheet for a period of time longer than 0 seconds but not longer than 90 seconds so that open circuit potentials are applied to the steel sheet in order of positive (+), negative (-), and positive (+), and the neutral salt electrolyte solution may include 100 g/l to 250 g/l of the sodium sulfate electrolyte.
  • the sulfuric acid electrolyte treatment may be performed by immersing the steel sheet in the sulfuric acid electrolyte solution maintained at 30°C to 60°C and applying a current of 10 A/dm 2 to 30 A/dm 2 to the steel sheet for 5 seconds to 50 seconds so that open circuit potentials are applied to the steel sheet in order of positive (+), negative (-), and positive (+), and the sulfuric acid electrolyte solution may include 50 g/l to 150 g/l of the sulfuric acid.
  • the steel sheet may have a gloss value of 130 or greater after being pickled through the process.
  • a mixed acid solution not including a nitric acid for removing Si oxide from a ferrite-based cold-rolled stainless steel sheet having 14% or less of chrome after a degreasing treatment and an annealing treatment the mixed acid solution including 70 g/l to 200 g/l of sulfuric acid, 1 g/l to 10 g/l of free hydrofluoric acid, and hydrogen peroxide, wherein the hydrogen peroxide and ion ions in the mixed acid solution satisfy the following concentration formula: [H 2 O 2 ] ⁇ 0.74 + 3.1e -[Fe]/1.1 + 3.2e -[Fe]/15 .
  • a ferrite-based cold-rolled stainless steel sheet can be pickled using the mixed acid solution not including nitric acid, and thus NOx and nitric nitrogen are not generated. Therefore, costs necessary for installing equipment for removing NOx and nitrogen can be saved.
  • ferrite-based cold-rolled stainless steel sheets pickled according to the present invention have higher quality than those pickled by methods according to the related art.
  • Si oxide can easily removed at a high rate of 3 g/m 2 -min to 15 g/m 2 -min in a mixed acid bath containing the mixed acid solution. Therefore, removing of Si oxide and flattening by the mixed acid solution can only be performed within 10 seconds to 100 seconds.
  • the solutions used in the pickling process of the present invention have simple compositions, the solutions can be easily handled and controlled to prevent reactions with substances other than surfaces of steel sheets. Therefore, cold-rolled stainless steel sheets having high surface qualities can be obtained, and high-speed production for improving productivity is possible.
  • the present invention provides a method of removing oxide scale from the surface of a low-chrome ferrite-based cold-rolled stainless steel sheet by immersing the steel sheet in a neutral salt electrolyte bath containing sodium sulfate as an electrolyte, a sulfuric acid electrolyte bath containing sulfuric acid as an electrolyte, and a mixed acid bath containing a pickling composition in which nitric acid is not included.
  • Oxide scale having a thickness of 100 nm to 300 nm is generally formed on a low-chrome ferrite-based cold-rolled stainless steel sheet after a heat treatment, and such oxide scale has a multilayer structure including a Cr-rich scale layer having more Cr oxide than Fe oxide, a Fe-rich scale layer having more Fe oxide than Cr oxide, and a Si-oxide layer formed between the oxide scale layers and the steel sheet.
  • the Cr-rich scale layer is removed in the neutral salt electrolyte bath.
  • the neutral salt electrolyte bath includes: a neural salt electrolyte solution having sodium sulfate as an electrolyte; and electrodes to apply a current to the surface of the steel sheet.
  • the electrodes are arranged so that surfaces of the steel sheet can be charged with potentials in order of positive (+), negative (-), and positive (+).
  • the Cr-rich scale layer is first dissolved as Cr 6+ , and thus the Cr-rich scale layer can be removed from the surface of the steel sheet.
  • sodium sulfate may be used as an electrolyte.
  • the sodium sulfate electrolyte increases the electrical conductivity of the electrolyte solution, which causes more current to flow in the steel sheet and thus facilitates dissolution of the Cr-rich scale layer.
  • the electrolyte solution may include 100 g/l to 250 g/l of a sodium sulfate electrolyte. If the concentration of the sodium sulfate electrolyte is 100 g/l or more, conductivity suitable for dissolving chrome can be obtained. However, if the concentration of the sodium sulfate electrolyte is greater than 250 g/l, sodium sulfate may precipitate in the electrolyte solution to clog equipment pipes and cause errors. Therefore, the concentration of the sodium sulfate electrolyte may be 250 g/l or less.
  • the electrical conductivity of the electrolyte in the neutral salt electrolyte bath is closely related to the temperature of the electrolyte solution. At a temperature of 50°C or higher, a conductivity level suitable for dissolving chrome may be obtained, and the conductivity increases as temperature increases. However, if the temperature of the electrolyte solution is greater than 90°C, it is difficult to practically control the temperature. Therefore, the temperature of the electrolyte solution in the neutral salt electrolyte bath may be set to be within a range of 50°C to 90°C.
  • a current of 10 A/dm 2 or higher may be applied through the electrodes for sufficiently eluting Cr of the Cr-rich scale layer.
  • a current of 10 A/dm 2 to 30 A/dm 2 may be applied so as not to increase initial equipment costs.
  • This neutral salt electrolyte treatment is performed within 90 seconds.
  • the neutral salt electrolyte treatment may be omitted, and Fe and Cr oxide scale may only be removed by a sulfuric acid electrolyte treatment. In this case, however, it may be necessary to perform the sulfuric acid electrolyte treatment and the next acid mixture treatment for longer periods of time. That is, the neutral salt electrolyte treatment may be necessary to decrease the total process time of a pickling treatment. If the neutral salt electrolyte treatment is performed for more than 90 seconds, over-pickling may occur to erode the steel sheet.
  • the Fe-rich scale layer is removed in the sulfuric acid electrolyte bath.
  • the sulfuric acid electrolyte bath includes: a sulfuric acid electrolyte solution having sulfuric acid as an electrolyte; and electrodes to apply a current to the surface of the steel sheet.
  • the electrodes are arranged so that the surface of the steel sheet can be charged with potentials in order of positive (+), negative (-), and positive (+).
  • the electrolyte solution may include 50 g/l to 150 g/l of sulfuric acid. If the concentration of the sulfuric acid is 50 g/l or more, appropriate conductivity may be maintained to maintain the amount of current flowing in the surface of the steel sheet at an appropriate level. However, if the concentration of the sulfuric acid is greater than 150 g/l, chemical dissolving may be dominant to roughen the surface of the steel sheet.
  • the sulfuric acid electrolyte solution may be maintained at 30°C or higher for maintaining conductivity equal to or higher than a lower limit.
  • the temperature of the sulfuric acid electrolyte solution may be set to be within a range of 30°C to 60°C.
  • a current of 10 A/dm 2 to 30 A/dm 2 may be applied to the sulfuric acid electrolyte bath. If a current of 10 A/dm 2 or lower is applied, the steel sheet may start to dissolve and become rough. In addition, since a large rectifier is necessary to apply a current greater than 30 A/dm 2 , a current of 10 A/dm 2 to 30 A/dm 2 may be applied so as not to increase initial equipment costs.
  • This sulfuric acid electrolyte treatment may be performed for 5 seconds to 50 seconds. If the sulfuric acid electrolyte treatment is performed for less than 5 seconds, pickling may be insufficient, and if the sulfuric acid electrolyte treatment is performed for longer than 50 seconds, over-pickling may occur. Thus, the sulfuric acid electrolyte treatment may be performed for the above-mentioned period of time.
  • the Si-oxide layer may be removed by a mixed acid solution not including nitric acid and nitrogen.
  • the mixed acid solution includes sulfuric acid, free hydrofluoric acid, and hydrogen peroxide.
  • the hydrofluoric acid and the sulfuric acid dissociate as shown in Reaction Formulas (1) and (2) below.
  • the hydrofluoric acid dissolves and dissociates, and the chemical equilibrium of the hydrofluoric acid is varied according to the concentration of H + generated by dissociation of the sulfuric acid, that is, according to the acidity of the mixed acid solution.
  • the hydrofluoric acid in its free state has acidity to dissolve Si oxide and dissolve Fe by permeating between the Si-oxide layer and the steel sheet. Dissolved Fe and Si ions are removed from the surface of the steel sheet in the form of FeF x (3-x) , H 2 SiF 6 , etc.
  • the concentration of the hydrofluoric acid in the mixed acid solution may be within the range of 1 g/l to 10 g/l, more specifically, within the range of 1 g/l to 5 g/l. If the concentration of the hydrofluoric acid is less than 1 g/l, the concentration of free hydrofluoric acid is not enough to dissolve Si, and thus the surface of the steel sheet may not be pickled. If the concentration of the hydrofluoric acid is greater than 10 g/l, the steel sheet may erode rapidly and become rough after pickling.
  • the concentration of the sulfuric acid is maintained at a predetermined value or above so as to prevent or reduce dissociation of the hydrofluoric acid.
  • the concentration of the sulfuric acid may be maintained within the range from 50 g/l to 150 g/l. If the concentration of the sulfuric acid is less than 50 g/l, it is difficult to maintain an effective concentration of free hydrofluoric acid, and thus acidity decreases as a result of hydrofluoric acid dissociation.
  • the concentration of the sulfuric acid is greater than 150 g/l, heat generated during sulfuric acid dilution may worsen working conditions. Therefore, the concentration of the sulfuric acid may be maintained within the above-mentioned range.
  • All the Si oxide of the oxide scale is formed on the surfaces and boundaries of ferrite grains of the ferrite-based stainless steel sheet, and the portion of the Si oxide formed on the boundaries of the ferrite grains is located deeper within the steel sheet than the other Si oxide.
  • Austenitic stainless steel starts to erode at its grain boundaries because of high corrosion resistance at grains.
  • the erosion rate of a ferrite-based steel sheet is not different at the insides and boundaries of grains because of low corrosion resistance at grains, and thus the surfaces and boundaries of grains are not selectively dissolved but dissolved together. Therefore, a considerable amount of the stainless steel sheet may dissolve until all the Si oxide is removed.
  • Fe 2+ comes out from the stainless steel sheet and is oxidized to Fe 3+ by reaction with hydrogen peroxide.
  • the Fe 3+ combines with HF to produce a complex, FeF x (3-x) .
  • Fe is removed from the stainless steel sheet.
  • Reaction Formulas (3) to (6) below, and the pickling process can be rapidly performed when the reactions smoothly occur.
  • Each kind of stainless steel has a unique potentiodynamic curve indicating a potential-current relationship, and the rate of pickling can be expressed according to current. That is, the maximum rate of pickling can be obtained by adjusting open circuit potential.
  • the open circuit potential of a cold-rolled steel sheet may be maintained at a range of - 0.2 V to 0.2 V. If the open circuit potential of a cold-rolled steel sheet is outside of this range, the cold-rolled steel sheet may not be pickled or may be defectively pickled, and even in the case that the cold-rolled steel sheet is pickled, the surface qualities thereof may be deteriorated.
  • a pickling process is performed while controlling the oxidation-reduction potential (ORP) of a pickling solution by varying the ratio of Fe 2+ /Fe 3+ in the pickling solution.
  • ORP oxidation-reduction potential
  • FIG. 3(a) there is no relationship between open circuit potential and ORP as shown in FIG. 3(a) . That is, ORP is not an important factor for open circuit potential in a pickling process.
  • open circuit potential relates to the concentration of metal ions generating in a mixed acid bath in a pickling process. That is, open circuit potential relates to the concentration of ions of iron, a parent material, and the concentration of hydrogen peroxide remaining in the mixed acid solution, especially, to the concentration of the remaining hydrogen peroxide.
  • the reaction expressed by Reaction formula (4) may not occur to increase the concentration of Fe 2+ locally on the surface of the steel sheet, and the reaction expressed by Reaction Formula (3) may mainly take place in the reverse direction.
  • substances such as Cu that had existed in the steel sheet or Fe as additives or impurities are re-deposited on the surface of the steel sheet as shown in Reaction Formula (6) to form black smut. Therefore, it is necessary to maintain the concentration of remaining hydrogen peroxide at a certain value or higher.
  • the concentration of the remaining hydrogen peroxide has a relationship with the concentration of iron ions in the mixed acid solution.
  • FIG. 3 shows the relationship between the open circuit potential of a cold-rolled steel sheet and the concentration of iron ions, and the minimum concentration of hydrogen peroxide necessary to maintain the open circuit potential of the cold-rolled steel sheet equal to or greater than -0.2 V in a mixed acid bath for performing a high-speed pickling process.
  • the open circuit potential of a steel sheet increases gradually as the concentration of iron ions increases.
  • Fe 3+ ions function as an oxidant, and as the concentration of Fe 3+ ions increases, the concentration of hydrogen peroxide necessary for maintaining the open circuit potential of the steel sheet is decreased.
  • the concentration of Fe 3+ ions is equal to or greater than a certain value, if the concentration of hydrogen peroxide is insufficient, the open circuit potential of the steel sheet becomes equal to or lower than -0.2 V to lower the surface qualities of the steel sheet.
  • the minimum concentration of hydrogen peroxide for maintaining the open circuit potential of a steel sheet equal to or higher than -0.2 V according to the concentration of iron ions can be expressed by the following formula.
  • [H 2 O 2 ] min 0.74 + 3.1e -[Fe]/1.1 + 3.2e -[Fe]/15
  • the concentration of hydrogen peroxide may be at least 7 g/l, and if the concentration of iron ions is 40 or higher, the concentration of hydrogen peroxide may be 1.0 g/l or higher.
  • the concentration of hydrogen peroxide is sufficiently high, it is unnecessary to add more hydrogen peroxide, simplifying the process.
  • the concentration of hydrogen peroxide may be kept lower than 30 g/l.
  • the temperature of the mixed acid solution is not limited to a certain value.
  • An operator can select an appropriate temperature range, for example, 20°C to 95°C, 25°C to 80°C, or 25°C to 65°C.
  • the concentrations of sulfuric acid, hydrofluoric acid, and remaining hydrogen peroxide are the most important factors increasing the effect and speed of the pickling process. Therefore, it is necessary to control the concentrations thereof.
  • the concentrations of sulfuric acid and hydrofluoric acid may be controlled using a typical acid analyzer, and the concentration of remaining hydrogen peroxide may be analyzed and controlled using a near-infrared analysis method or an automatic titration method.
  • a pickling process can be rapidly performed within about 15 seconds to about 240 seconds to markedly reduce the time necessary for pickling, and low-chrome ferrite-based cold-rolled stainless steel sheets having superior quality can be produced.
  • a neutral salt electrolyte treatment and a sulfuric acid electrolyte treatment in a pickling process for removing oxide scale were checked.
  • a Cr-rich scale layer and a Fe-rich scale layer were removed from a ferrite-based cold-rolled stainless steel sheet having 14% or less of chrome through the neutral salt electrolyte treatment and the sulfuric acid electrolyte treatment.
  • a neutral salt electrolyte solution including 150 g/l of sodium sulfate as an electrolyte was maintained at 60°C, and a current of 150 A/dm 2 was applied for 40 seconds.
  • a pH-1 sulfuric acid electrolyte solution including 85 g/l of sulfuric acid was maintained at 50°C, and a current of 20 A/dm 2 was applied for 15 seconds in a manner such that the steel sheet was charged with potentials in order of positive (+), negative (-), and positive (+).
  • FIGS. 1 (a) and 1(b) The surface of the steel sheet treated with the neutral salt electrolyte treatment and the sulfuric acid electrolyte treatment, and the surface of a non-treated steel sheet were captured with a scanning electron microscope (SEM) and shown in FIGS. 1 (a) and 1(b).
  • FIG. 1 (a) shows the surface of the electrolyte-treated steel sheet
  • FIG. 1(b) shows the surface of the non-treated steel sheet.
  • both (Cr,Fe) 3 O 4 and silicon oxide remain on the surface of the steel sheet not treated through the neutral salt electrolyte treatment and the sulfuric acid electrolyte treatment. However, only silicon oxide remains on the surface of the treated steel sheet.
  • Ferrite-based cold-rolled stainless steel sheets having 14% or less of chrome and treated as explained in Example 1 to remove Fe-rich and Cr-rich scale layers were heat-treated at 900°C and used as samples for observing a relationship between the surface states and open circuit potentials of the samples.
  • the samples were immersed in a mixed acid solution maintained at 45°C and including 150 g/l sulfuric acid and 5 g/l of free hydrofluoric acid, and a pickling process was performed by applying potentials of -0.5 V to 0.5 V to the samples for 150 seconds as shown in Table 1.
  • the surface states of the samples were observed using a SEM, and pickling and surface roughness of the samples were evaluated. If scale remained on a sample, the sample was determined as being not pickled. If the surface roughness of a sample was 3 ⁇ m or greater, the sample was determined as having bad surface roughness, indicted by "X,” and if the surface roughness of a sample is 3 ⁇ m or less, the sample was determined as having good surface roughness, indicated by "O.” Samples determined as being not pickled were not evaluated in surface roughness.
  • Comparative Sample 3 had poor surface roughness. That is, it can be understood that the surface of Inventive Sample 2 dissolved uniformly along grains as shown in FIG. 2(a) but the surface of Comparative Sample 3 had poor surface qualities due to separation of grains along grain surfaces as shown in FIG. 2 (b) .
  • open circuit potentials of -0.2 V to 0.2 V are suitable for dissolving Si oxide layers.
  • This example is for checking the relationship between the concentrations of hydrogen peroxide and iron ions for obtaining an open circuit potential of -0.2 V in a mixed acid treatment for a ferrite-based cold-rolled stainless steel sheet.
  • the ferrite-based cold-rolled stainless steel sheet having 14% or less of chrome and treated as explained in Example 1 to remove Fe-rich and Cr-rich scale layers was heat-treated at 900°C and used as a sample.
  • the sample was immersed in a mixed acid solution maintained at 45°C and including 150 g/l sulfuric acid and 5 g/l of free hydrofluoric acid, and the open circuit potential of the sample was measured while adding metal ions (Fe 3+ ) and hydrogen peroxide to the mixed acid solution.
  • the open circuit potential of the sample was measured with respect to the concentration of iron ions, and the minimum concentration of hydrogen peroxide for maintaining the open circuit potential equal to or greater than -0.2 V was measured with respect to the concentration of iron ions.
  • FIG. 3 shows the measured results.
  • FIG. 4 is a graph showing a relationship between the minimum concentration of hydrogen peroxide and the concentration of iron ions for maintaining the open circuit potential of the sample equal to or greater than -0.2 V.
  • concentration of iron ions increases, the minimum concentration of hydrogen peroxide for maintaining the open circuit potential of the sample is reduced.
  • concentration of iron ions increases to 40 g/l or greater, the minimum concentration of hydrogen peroxide is not reduced to 1 g/l or less.
  • This example is for checking appropriate conditions for a neutral salt electrolyte treatment.
  • a neutral salt electrolyte treatment was performed in the same method as in Example 1. However, the temperature of an electrolyte solution in a bath, a current, and the concentration of sodium sulfate were varied as shown in Table 2.
  • the surface qualities of the steel sheets were good when the neutral salt electrolyte treatment was performed under conditions where the temperature of the electrolyte solution was from 50°C to 90°C, the concentration of sodium sulfate in the electrolyte solution was from 100 g/l to 250 g/l, and current density was 10 A/dm 2 to 30 A/dm 2 .
  • This example is for checking appropriate conditions for a sulfuric acid electrolyte treatment.
  • a sulfuric acid electrolyte treatment was performed in the same manner as in Example 1. However, the temperature of an electrolyte solution in a bath, a current, and the concentration of sulfuric acid were varied as shown in Table 3.
  • the surface quality of the steel sheets was good when the sulfuric acid electrolyte treatment was performed under the conditions where the temperature of the electrolyte solution was from 30°C to 60°C, the concentration of sulfuric acid in the electrolyte solution was from 50 g/l to 150 g/l, and the current density was 10 A/dm 2 to 30 A/dm 2 .
  • This example is for checking appropriate treatment periods of time for a neutral salt electrolyte treatment and a sulfuric acid electrolyte treatment.
  • a neutral salt electrolyte treatment and a sulfuric acid electrolyte treatment were performed in the same method as in Example 1 except that treatment periods of time were as shown in Table 4.
  • This example is for checking appropriate treatment conditions for a mixed acid bath.
  • Example 3 Steel sheets treated through a neutral salt electrolyte treatment and a sulfuric acid electrolyte treatment as explained in Example 1 were treated using a mixed acid solution under the conditions shown in Table 5.
  • the mixed acid solution was maintained at room temperature, and the concentration of hydrogen peroxide was controlled as explained in Example 3.
  • steel sheets may properly pickled when the steel sheets are immersed for 10 seconds to 100 seconds in a mixed acid solution including 70 g/l to 200 g/l of sulfuric acid, 1 g/l to 10 g/l of free hydrofluoric acid, and at least 1.0 of hydrogen peroxide, although the concentration of hydrogen peroxide varies according to the concentration of iron ions.
  • the quality of ferrite-based cold-rolled stainless steel sheets pickled according to the present invention by using a mixed acid solution including sulfuric acid, hydrofluoric acid, and hydrogen peroxide was compared with the quality of a ferrite-based cold-rolled stainless steel sheet pickled according to a method of related art by using a mixed acid solution including nitric acid and hydrofluoric acid.
  • Process conditions and compositions of the acid solutions are as follows.
  • Comparative Sample 1 a ferrite-based cold-rolled stainless steel sheet was treated through a neutral salt electrolyte treatment and a sulfuric acid electrolyte treatment as explained in Example 1, and was then immersed in a mixed acid solution including 100 g/l of nitric acid and 3 g/l of hydrofluoric acid for 30 seconds. Then, the gloss thereof was measured.
  • Inventive Sample 1 the gloss of Inventive Sample 4 of Example 7 was measured.
  • Inventive Sample 2 the gloss of Inventive Sample 2 of Example 7 was measured.
  • the measured gloss values of the samples are shown in FIG. 5 .
  • the gloss of the ferrite-based cold-rolled stainless steel sheets pickled by the mixed acid pickling method of the present invention can be compared with the gloss of the ferrite-based cold-rolled stainless steel sheet pickled by a nitric acid pickling method of the related art or the gloss of a non-pickled ferrite-based cold-rolled stainless steel sheet.
  • the gloss of Inventive Samples is 130 or higher, greater than the gloss of Comparative Sample 1 by about 40 to about 60.
  • the pickling method of the present invention is useful for improving the surface quality of steel sheets.

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

Claims (8)

  1. Procédé de décapage d'une tôle en acier inoxydable laminée à froid à base de ferrite à faible teneur en chrome ayant 14 % en poids ou moins de chrome après un traitement de dégraissage et un traitement de recuit, le procédé comprenant :
    la réalisation d'un traitement par électrolyte d'acide sulfurique pour éliminer la calamine d'oxyde de Fe et de Cr de la tôle en acier inoxydable laminée à froid à base de ferrite à faible teneur en chrome en utilisant une solution d'électrolyte d'acide sulfurique comprenant un acide sulfurique en tant qu'électrolyte ; et
    la réalisation d'un traitement par acide mixte dans lequel la tôle en acier inoxydable laminée à froid à base de ferrite à faible teneur en chrome est immergée dans une solution d'acide mixte ne contenant pas d'acide nitrique tout en comprenant un acide sulfurique, un acide fluorhydrique libre et un peroxyde d'hydrogène,
    dans lequel la solution d'acide mixte comprend 70 g/l à 200 g/l d'acide sulfurique et 1 g/l à 10 g/l d'acide fluorhydrique libre,
    dans lequel la solution d'acide mixte comprend initialement 7 g/l ou plus du peroxyde d'hydrogène et aucun ion Fe,
    dans lequel le peroxyde d'hydrogène et les ions Fe satisfont la formule de concentration suivante :

            [H2O2] ≥ 0,74 + 3,1e-[Fe]/1,1 + 3,2e-[Fe]/15.

  2. Procédé de décapage selon la revendication 1, dans lequel un potentiel en circuit ouvert de la tôle en acier inoxydable laminée à froid immergée dans la solution d'acide mixte est maintenu dans une plage de - 0,2 V à 0,2 V.
  3. Procédé de décapage selon la revendication 1, dans lequel la tôle en acier inoxydable laminée à froid est immergée dans la solution d'acide mixte pendant 10 secondes à 100 secondes.
  4. Procédé selon la revendication 1, comprenant en outre la réalisation d'un traitement par électrolyte de sel neutre pour éliminer la calamine riche en Cr ayant davantage d'oxyde de Cr que d'oxyde de Fe de la tôle en acier en utilisant une solution d'électrolyte de sel neutre comprenant un électrolyte de sulfate de sodium.
  5. Procédé selon la revendication 4, dans lequel le traitement par électrolyte de sel neutre est réalisé en immergeant la tôle en acier dans la solution d'électrolyte de sel neutre maintenue à 50 °C à 90 °C et en appliquant un courant de 10 A/dm2 à 30 A/dm2 à la tôle en acier pendant une période de plus de 0 seconde mais de pas plus de 90 secondes de sorte que des potentiels en circuit ouvert soient appliqués à la tôle en acier dans l'ordre positif (+), négatif (-) et positif (+).
  6. Procédé selon la revendication 4, dans lequel la solution par électrolyte de sel neutre comprend 100 g/l à 250 g/l de l'électrolyte de sulfate de sodium.
  7. Procédé selon la revendication 1, dans lequel le traitement d'électrolyte d'acide sulfurique est réalisé en immergeant la tôle en acier dans la solution d'électrolyte d'acide sulfurique maintenue à 30 °C à 60 °C et en appliquant un courant de 10 A/dm2 à 30 A/dm2 à la tôle en acier pendant 5 secondes à 50 secondes de sorte que des potentiels en circuit ouvert soient appliqués à la tôle en acier dans l'ordre positif (+), négatif (-) et positif (+).
  8. Procédé selon la revendication 7, dans lequel la solution d'électrolyte d'acide sulfurique comprend 50 g/l à 150 g/l de l'acide sulfurique.
EP11852757.1A 2010-12-28 2011-12-27 Procédé de décapage rapide, écologique, de production de tôle d'acier inoxydable à base de ferrite et à faible teneur en chrome, laminée à froid doté de qualité de surface supérieure Active EP2660364B1 (fr)

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KR20100136140 2010-12-28
KR1020110120187A KR101289147B1 (ko) 2010-12-28 2011-11-17 표면품질이 우수한 저크롬 페라이트계 스테인리스 냉연강판을 제조하기 위한 친환경 고속 산세 프로세스
PCT/KR2011/010157 WO2012091412A2 (fr) 2010-12-28 2011-12-27 Procédé de décapage rapide, écologique, de production de tôle d'acier inoxydable à base de ferrite et à faible teneur en chrome, laminée à froid doté de qualité de surface supérieure

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EP2660364A2 EP2660364A2 (fr) 2013-11-06
EP2660364A4 EP2660364A4 (fr) 2014-08-13
EP2660364B1 true EP2660364B1 (fr) 2016-03-09

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KR101353856B1 (ko) * 2012-07-31 2014-01-21 주식회사 포스코 오스테나이트계 스테인리스 냉연강판을 제조하기 위한 저온 고속 산세 프로세스
KR101359098B1 (ko) * 2012-07-31 2014-02-12 주식회사 포스코 오스테나이트계 스테인리스 냉연강판을 제조하기 위한 고속 산세 프로세스
KR101382934B1 (ko) * 2012-07-31 2014-04-17 주식회사 포스코 내식성 향상을 위한 오스테나이트계 스테인리스 냉연강판의 고속 산세 프로세스
CN103243339B (zh) * 2013-04-16 2016-03-09 山西太钢不锈钢股份有限公司 一种中铬超纯铁素体不锈钢连续退火酸洗方法
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CN103403230A (zh) 2013-11-20
WO2012091412A2 (fr) 2012-07-05
CN103403230B (zh) 2016-02-24
KR101289147B1 (ko) 2013-07-23
WO2012091412A3 (fr) 2012-10-04
EP2660364A4 (fr) 2014-08-13
EP2660364A2 (fr) 2013-11-06
JP5768141B2 (ja) 2015-08-26
KR20120075344A (ko) 2012-07-06
WO2012091412A4 (fr) 2012-11-22
JP2014501337A (ja) 2014-01-20

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