EP3666931A1 - Procédé de fabrication d'une bande métallique ayant un revêtement de chrome et d'oxyde de chrome avec un électrolyte à base de chromium trivalent - Google Patents

Procédé de fabrication d'une bande métallique ayant un revêtement de chrome et d'oxyde de chrome avec un électrolyte à base de chromium trivalent Download PDF

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Publication number
EP3666931A1
EP3666931A1 EP19206950.8A EP19206950A EP3666931A1 EP 3666931 A1 EP3666931 A1 EP 3666931A1 EP 19206950 A EP19206950 A EP 19206950A EP 3666931 A1 EP3666931 A1 EP 3666931A1
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EP
European Patent Office
Prior art keywords
electrolysis
chromium
tanks
coating
chromium oxide
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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.)
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EP19206950.8A
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German (de)
English (en)
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EP3666931B1 (fr
Inventor
Andrea Dr. Marmann
Christoph Molls
Rainer Görtz
Thomas Lenz
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ThyssenKrupp AG
ThyssenKrupp Rasselstein GmbH
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ThyssenKrupp AG
ThyssenKrupp Rasselstein GmbH
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/38—Chromatising
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • C25D7/0628—In vertical cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/16—Apparatus for electrolytic coating of small objects in bulk
    • C25D17/28—Apparatus for electrolytic coating of small objects in bulk with means for moving the objects individually through the apparatus during treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/02—Heating or cooling
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/10—Agitating of electrolytes; Moving of racks
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces

Definitions

  • the invention relates to a method for producing a metal strip coated with a coating of chromium and chromium oxide according to the preamble of claim 1.
  • steel sheets are known from the prior art electrolytically coated with a coating of chromium and chromium oxide, which are referred to as tin-free steel sheet ("Tin Free Steel", TFS) or as “Electrolytic Chromium Coated Steel (ECCS)” and one Show alternative to tinplate.
  • TFS Tin Free Steel
  • ECCS Electrolytic Chromium Coated Steel
  • These tin-free steel sheets are particularly characterized by their good adhesion for paints or organic protective coatings (such as polymer coatings made of PP or PET).
  • these chromium-coated steel sheets have good corrosion resistance and good processability in forming processes for the production of packaging, for example in deep-drawing and ironing processes.
  • electrolytic coating methods are known from the prior art, with which the coating is applied in a coil coating system to a strip-shaped steel sheet using an electrolyte containing chromium VI.
  • these coating processes have considerable disadvantages due to the environmental and health-endangering properties of the chromium-VI-containing electrolytes used in the electrolysis process and must be replaced by alternative coating processes in the foreseeable future, since the use of chromium-VI-containing materials will be prohibited in the future.
  • a method for the electrolytic coating of an electrically conductive substrate which is in particular a black plate (uncoated steel plate) or a tin plate (tinned steel sheet) can act, known with a chrome metal-chromium oxide (Cr-CrOx) layer, in which the substrate, connected as a cathode, is brought into contact with an electrolytic solution which contains a trivalent chromium compound (Cr-III), an anode is provided which prevents or at least reduces the oxidation of chromium (III) ions to chromium (VI) ions and removes hydrogen bubbles which arise during the electrodeposition of the coating on the surface of the substrate.
  • Cr-CrOx chrome metal-chromium oxide
  • Cr-III trivalent chromium compound
  • the deposition reaction and the surface properties of the electrodeposited coating depend on the temperature of the electrolytic solution and that temperatures of the electrolytic solution between 30 ° C and 70 ° C are suitable to produce coatings with a good surface appearance.
  • a preferred temperature range between 40.degree. C. and 60.degree. C. has been recognized as being advantageous in relation to an efficient deposition reaction because the electrolyte solution has good conductivity at these temperatures.
  • composition of the coating which, depending on the components contained in the electrolytic solution in addition to the trivalent chromium compound (Cr-III), can also contain chromium sulfates and chromium carbides in addition to the components chromium metal and chromium oxide, depends very much on the current densities of the electrolysis depends on which are set at the anodes during the electrolytic deposition process in the electrolytic tanks in which the electrolytic solution is contained.
  • the coating contains a higher one Proportion of chromium oxide, which in the range of higher current densities accounts for between 1 ⁇ 4 and 1/3 of the total weight of the coating.
  • the values of the current density thresholds which delimit the areas (regimes I to III) depend on the belt speed at which the steel sheet is moved through the electrolyte solution.
  • the object of the present invention is to provide a process which is as efficient as possible and which can be carried out on a large scale in a coil coating installation for producing a metal strip coated with a coating of chromium and chromium oxide on the basis of an electrolyte solution with a trivalent chromium compound, the coating having the highest possible proportion of chromium oxide to ensure sufficient corrosion resistance of the coated metal strip and a good adhesive base for organic coatings, such as To achieve lacquers or polymer films made of PET or PP.
  • a coating which contains chromium metal and chromium oxide is applied electrolytically from an electrolyte solution which contains a trivalent chromium compound to a metal strip, in particular a steel strip, by bringing the metal strip into contact with the electrolyte solution as a cathode the metal strip is passed in succession at a predetermined strip speed in a strip running direction through a plurality of electrolysis tanks arranged one behind the other in the strip running direction, the electrolyte solution having a temperature averaged over the volume of the electrolysis tank, at least in the last electrolysis tank seen in the strip running direction or in a rear group of electrolysis tanks is less than 40 ° C and the electrolysis time in which the metal strip is in electrolytically effective contact with the electrolytic solution in the last electrolysis tank or in the rear group of electrolysis tanks is less than 2.0 seconds.
  • the temperature of the electrolyte solution in the last electrolysis tank or in the rear group of electrolysis tanks, as seen in the direction of travel of the belt, is
  • the mean temperature in each case is the average temperature that results over the entire volume of an electrolysis tank. There is usually a temperature gradient in the electrolysis tanks with an increase in temperature from top to bottom.
  • chromium oxide we mean all oxide forms of chromium (CrOx), including chromium hydroxides, in particular chromium (III) hydroxide and chromium (III) oxide hydrate, as well as mixtures thereof.
  • the electrolysis time in which the metal strip is in electrolytically effective contact with the electrolyte solution is expediently less than 2 seconds in each of the electrolysis tanks, so that the metal strip can be guided at a constant strip speed through the plurality of electrolysis tanks which are arranged one behind the other in the strip running direction and which are expediently of identical design.
  • the electrolysis time in each of the electrolysis tanks is preferably between 0.5 and 2.0 seconds, in particular between 0.6 seconds and 1.8 seconds.
  • the electrolysis time in each of the electrolysis tanks can also be between 0.3 and 2.0 seconds and preferably between 0.5 seconds and 1.4 seconds.
  • the total electrolysis time (t E ) in which the metal strip is in electrolytically effective contact with the electrolyte solution is preferably between 2 and 16 seconds and in particular between 4 seconds and 14 seconds across all electrolysis tanks.
  • the temperature of the electrolytic solution in the first electrolytic tank or in the front group of electrolytic tanks may be higher than in the last electrolytic tank.
  • the temperature of the electrolyte solution in the first electrolysis tank or in the front group of electrolysis tanks is expediently more than 50.degree. C. and in particular between 53.degree. C. and 70.degree. C., since in this temperature range chromium is deposited more efficiently, in particular in the form of chromium metal , can be observed.
  • a coating is deposited on the surface of the metal strip which comprises at least a lower and an upper layer, the lower layer in the first electrolysis tank or in the front group of electrolysis tanks and the upper layer in the last electrolysis tank or in the rear group of electrolysis tanks is deposited and the lower layer has a small proportion of chromium oxide and the upper layer has a higher proportion of chromium oxide.
  • the proportion by weight of chromium oxide in the lower layer facing the surface of the metal strip is preferably less than 15% and in the upper layer preferably more than 40%.
  • a uniform temperature of the electrolyte solution in the electrolysis tanks which (averaged over the volume of the respective electrolysis tank) in all electrolysis tanks preferably between 20 ° C. and less than 40 ° C. and particularly preferably between 25 ° C and 38 ° C.
  • the electrolyte solution in the electrolysis tanks has to be cooled in order to maintain the preferred temperatures. This is made more difficult by the fact that the circulatory systems of the electrolysis tanks are usually coupled. It can therefore be expedient for apparatus reasons to maintain the same temperature in each case in the electrolysis tanks in order to avoid a different setting which is complex in terms of equipment. From a result-oriented point of view, in particular with regard to improved corrosion resistance of the coated metal strip, it is advantageous, however, to set a higher temperature in the first electrolysis tank or in the front group of electrolysis tanks than in the last electrolysis tank or in the rear group of electrolysis tanks.
  • the metal strip is guided at least through a first electrolysis tank or a front group of electrolysis tanks and then through a second electrolysis tank or a rear group of electrolysis tanks, the average temperature of the electrolyte solution in the first electrolysis tank or the front group of electrolysis tanks is greater than the average temperature of the electrolytic solution in the second electrolysis tank or the rear group of electrolysis tanks.
  • the metal strip is first passed through a first electrolysis tank or a front group of electrolysis tanks, then through a second electrolysis tank or a middle group of electrolysis tanks and finally through a last electrolysis tank or a rear group of electrolysis tanks, the average temperature being the Electrolyte solution in the first electrolysis tank or the front group of electrolysis tanks and / or in the second electrolysis tank or the middle group of electrolysis tanks is greater than the average temperature of the electrolyte solution in the last electrolysis tank or the rear group of electrolysis tanks.
  • the composition of the coating deposited electrolytically on the metal strip depends not only on the temperature of the electrolytic solution but also on the current density of the electrolysis process. It has been shown that at higher current densities, which are in the region of Regime III, where a (partial) decomposition of the applied coating is already taking place, a higher proportion of the chromium oxide is produced in the coating compared to the lower current densities in Regime II, where a linear relationship can be observed between the deposited weight of the chromium and the current density.
  • the current densities j 1 , j 2 and j 3 are increased, so that, for example at a belt speed of 300 m / min, the current densities j 1 and j 2 are greater than 70 A / dm 2 and the high current density j 3 is greater than 130 A / dm 2 .
  • a particularly preferred embodiment provides for a lower current density in the first electrolysis tank or in the front group of electrolysis tanks compared to the second electrolysis tank following in the direction of travel of the belt or in the middle group of electrolysis tanks, so that the relation 20 A / dm 2 ⁇ j 1 ⁇ j 2 ⁇ j 3 applies.
  • a coating can be deposited on the surface of the metal strip, which is composed of three layers with different compositions with respect to their proportion of chromium metal and chromium oxide, the lower layer facing the metal strip having an average proportion by weight of chromium oxide, which in particular in the Is in the range from 10% to 15%, the middle layer has a low proportion by weight of chromium oxide, which is in particular in the range from 2% to 10%, and the upper layer has a high proportion by weight of chromium oxide, which is in particular more than 30%, is preferably more than 50%.
  • the coating having the chromium oxide content of at least 5 mg / m 2 , preferably more than 7 mg / m 2 , required for adequate corrosion resistance.
  • the total weight of the chromium oxide preferably does not exceed 15 mg / m 2 , since with higher weights of the chromium oxide a reduced adhesion of organic coatings made of lacquers or thermoplastic polymer materials is observed. For this reason, a preferred range for the chromium oxide weight support is between 5 and 15 mg / m 2 .
  • a certain proportion by weight of the total coating which is approximately 9 to 15%, is due to the chromium oxide Chromium oxide crystals already form on the surface of the metal strip in the first electrolysis tank or in the front group of electrolysis tanks and in the second electrolysis tank or in the middle group of electrolysis tanks.
  • chromium oxide crystals act in the last electrolysis tank and / or in the rear group of electrolysis tanks as a germ cell for the growth of further oxide crystals, which is why the efficiency of the deposition of chromium oxide or the proportion of chromium oxide in the total coating layer in the last electrolysis tank or in the rear group of electrolysis tanks increases.
  • a sufficiently high coating of chromium oxide of preferably more than 5 mg / m 2 on the surface of the Metal bands are generated.
  • the proportion of chromium oxide produced in the first electrolysis tank or in the front group of electrolysis tanks and in the second electrolysis tank or in the middle group of electrolysis tanks forms with higher current densities (and consequently lower oxide proportion) due to the higher proportion of oxygen in the coating compared to electrolytic deposition ) a denser coating, which leads to improved corrosion resistance.
  • a current density of at least 20 A / dm 2 is required to maintain a preferred strip speed of at least 100 m / min, so that a chromium-chromium oxide layer can be deposited on at least one surface of the metal strip.
  • This current density of 20 A / dm 2 is the first Current density threshold at a belt speed of approx. 100 m / min, which delimits regime I (no chrome deposition) from regime II (chrome deposition with a linear relationship between current density and the chrome weight support of the deposited coating).
  • the current densities (j 1 , j 2 , j 3 ) in the electrolysis tanks are each adapted to the belt speed, with at least essentially a linear relationship between the belt speed and the respective current density (j 1 , j 2 , j 3 ). It is advantageous if the current density in the first electrolysis tank or in the front group of electrolysis tanks is lower than in the second electrolysis tank or in the middle group of electrolysis tanks.
  • a lower current density in the first electrolysis tank or in the front group of electrolysis tanks produces a dense and therefore corrosion-resistant chromium-chromium oxide coating with a relatively high chromium oxide content, preferably at more than 8%, in particular between 8 and 15%, and directly on the surface of the metal strip is particularly preferably more than 10% by weight.
  • At least one pair of anodes with two opposite anodes is expediently arranged in each electrolysis tank, the metal strip passing between the opposite anodes of an anode pair.
  • This enables a uniform current density distribution to be achieved around the metal strip.
  • the anode pairs of each electrolysis tank can be supplied with electrical current independently of one another, so that different current densities (j 1 , j 2 , j 3 ) can be set in the electrolysis tanks.
  • the strip speed of the metal strip is expediently chosen so that the electrolysis time (t E ) in which the metal strip is in electrolytically effective contact with the electrolyte solution is less than 1.0 seconds in each of the electrolysis tanks and in particular between 0.5 and 1, 0 seconds and is preferably between 0.6 seconds and 0.9 seconds.
  • the coating deposited on the metal strip with the method according to the invention preferably has a chromium weight support of at least 40 mg / m 2 and in particular from 70 mg / m 2 to 180 mg / m 2 in order to achieve sufficient corrosion resistance of the coated metal strip.
  • the one contained in the coating The proportion by weight of chromium oxide in the total weight of the coating is preferably at least 5%, in particular more than 10% and, for example, between 11 and 16%.
  • the chromium oxide portion of the coating has a weight of chromium bound as chromium oxide of at least 3 mg Cr per m 2 , in particular from 3 to 15 mg / m 2 and preferably at least 7 mg Cr per m 2 .
  • a single electrolyte solution is expediently used in the method according to the invention, i.e. the electrolysis tanks are all filled with the same electrolyte solution.
  • a preferred composition of the electrolytic solution comprises basic Cr (III) sulfate (Cr 2 (SO 4 ) 3 ) as a trivalent chromium compound.
  • concentration of the trivalent chromium compound in the electrolyte solution is both in this preferred composition and in other compositions at least 10 g / l and preferably more than 15 g / l and in particular is 20 g / l or more.
  • Further useful constituents of the electrolyte solution can be complexing agents, in particular an alkali metal carboxylate, preferably a salt of formic acid, in particular potassium format or sodium format.
  • the ratio of the proportion by weight of the trivalent chromium compound to the proportion by weight of the complexing agents, in particular the formates, is preferably between 1: 1.1 and 1: 1.4 and preferably between 1: 1.2 and 1: 1.3 and in particular 1: 1 , 25
  • the electrolytic solution can comprise an alkali metal sulfate, preferably potassium or sodium sulfate.
  • the electrolyte solution is preferably free of halides, in particular free of chloride and bromide ions and free of a buffering agent and in particular free of a boric acid buffer.
  • the pH of the electrolyte solution (measured at a temperature of 20 ° C.) is preferably between 2.0 and 3.0 and particularly preferably between 2.5 and 2.9 and in particular 2.7.
  • An acid for example sulfuric acid, can be added to adjust the pH of the electrolyte solution.
  • an organic coating in particular a lacquer or a thermoplastic material, for example a polymer film made of PET, PE, PP or a mixture thereof, can be applied to the surface of the chromium metal and chromium oxide coating for additional protection against corrosion and a barrier against acidic contents of packaging.
  • the metal strip can be a (initially uncoated) steel strip (black plate strip) or a tinned steel strip (tin plate strip).
  • FIG. 1 a coil coating system for carrying out the method according to the invention is shown schematically in a first embodiment.
  • the coil coating system comprises three electrolysis tanks 1a, 1b, 1c arranged side by side or one behind the other, each of which is filled with an electrolyte solution E.
  • An initially uncoated metal strip M in particular a steel strip, is passed through the electrolysis tanks 1a-1c in succession.
  • the metal strip M is drawn through a transport device, not shown here, into a strip running direction v at a predetermined strip speed through the electrolysis tanks 1a-1c.
  • Current rolls S are arranged above the electrolysis tanks 1a-1c, via which the metal strip M as Cathode is switched.
  • a deflection roller U is also arranged in each electrolysis tank, around which the metal strip M is guided and is thereby directed into and out of the electrolysis tank.
  • At least one anode pair AP is arranged in each electrolysis tank 1a-1c below the liquid level of the electrolyte solution E.
  • two anode pairs AP arranged one behind the other in the strip running direction are provided in each electrolysis tank 1a-1c.
  • the metal strip M is passed between the opposite anodes of an anode pair AP.
  • Two anode pairs AP are thus arranged in each electrolysis tank 1a, 1b, 1c in such a way that the metal strip M is passed through these anode pairs AP in succession.
  • the last anode pair APc in the downstream direction of the last electrolysis tank 1c seen in the strip running direction v has a shortened length in comparison to the other anode pairs AP. As a result, a higher current density can be generated with this last anode pair APc when an equally high electrical current is applied.
  • the metal strip M can be a cold-rolled, initially uncoated steel strip (black plate strip) or a tinned steel strip (tin plate strip).
  • black plate strip black plate strip
  • tinned steel strip tin plate strip
  • the metal strip M is first degreased, rinsed, pickled and rinsed again and passed in this pretreated form through the electrolysis tanks 1 a - 1 c, the metal strip M being switched as a cathode by supplying electrical current via the current rollers S.
  • the belt speed at which the metal belt M is passed through the electrolysis tanks 1a-1c is at least 100 m / min and can be up to 900 m / min.
  • the same electrolyte solution E is filled in each of the electrolysis tanks 1a-1c arranged one behind the other in the direction of tape travel v.
  • the electrolytic solution E contains a trivalent chromium compound, preferably basic Cr (III) sulfate [Cr 2 (SO 4 ) 3 ].
  • the electrolyte solution preferably contains at least one complexing agent, for example a salt of formic acid, in particular potassium or sodium format.
  • the ratio of the proportion by weight of the trivalent chromium compound to the proportion by weight of the complexing agents, in particular the formats, is preferably between 1: 1.1 and 1: 1.4 and particularly preferably 1: 1.25.
  • the Electrolyte solution E contain an alkali metal sulfate, for example potassium or sodium sulfate.
  • concentration of the trivalent chromium compound in the electrolyte solution E is at least 10 g / l and particularly preferably 20 g / l or more.
  • the temperature of the electrolyte solution E can be the same in all electrolysis tanks 1a-1c and, according to the invention, is at most 40 ° C. In preferred exemplary embodiments of the method according to the invention, however, different temperatures of the electrolyte solution can also be set in the electrolysis tanks 1a-1c.
  • the temperature of the electrolyte solution in the last electrolysis tank 1c can be at most 40 ° C. and a higher temperature can be present in the electrolysis tanks 1a and 1b arranged upstream.
  • the temperature of the electrolytic solution in the last electrolysis tank 1c is preferably between 25 ° C. and 37 ° C. and in particular 35 ° C.
  • the temperature of the electrolyte solution in the first two electrolysis tanks 1a, 1b in this exemplary embodiment is preferably between 50 ° C. and 75 ° C. and in particular 55 ° C. Due to the lower temperature of the electrolytic solution E, the deposition of a chromium / chromium oxide layer with a higher proportion of chromium oxide is promoted in the last electrolysis tank 1c.
  • the metal strip M which is connected as the cathode and passed through the electrolysis tanks 1a-1c, is in electrolytic contact with the electrolyte solution E during an electrolysis time t E.
  • the electrolysis time is in each of the electrolysis tanks 1 a, 1b, 1c preferably between 0.5 and 2.0 seconds.
  • belt speeds are set so high that the electrolysis time t E in each electrolysis tank 1a, 1b, 1c is less than 2 seconds and is in particular between 0.6 seconds and 1.8 seconds.
  • the total electrolysis time in which the metal strip M is in electrolytically effective contact with the electrolyte solution E across all electrolysis tanks 1a-1c is accordingly between 1.8 and 5.4 seconds.
  • the anode pairs AP arranged in the electrolysis tanks 1a-1c can be supplied with direct electrical current in such a way that the same current density is present in the electrolysis tanks 1a, 1b, 1c.
  • direct electrical current in such a way that the same current density is present in the electrolysis tanks 1a, 1b, 1c.
  • a low current density j 1 can be set in the first electrolysis tank 1a upstream in the direction of tape travel v, a medium current density j 2 in the second electrolysis tank 1b in the direction of tape travel and a high current density j 3 in the last electrolysis tank 1c in the direction of tape travel , so that the relation j 1 ⁇ j 2 ⁇ j 3 applies and the low current density j 1 > 20 A / dm 2 .
  • the current densities set in the electrolysis tanks 1a-1c electrolytically deposit a layer containing chromium metal and chromium oxide on at least one side of the metal strip M, a layer B1, B2, B3 being produced in each of the electrolysis tanks 1a, 1b, 1c. Due to the different current densities j 1 , j 2 , j 3 in the individual electrolysis tanks 1a, 1b, 1c, each electrolytically applied layer B1, B2, B3 has a different composition, which differs in particular by the proportion of chromium oxide.
  • FIG 3 a sectional illustration of a metal strip M electrolytically coated on one side with the method according to the invention is shown schematically.
  • a coating B is applied to one side of the metal strip M and is composed of the individual layers B1, B2, B3.
  • Each individual layer B1, B2, B3 is applied to the surface in one of the electrolysis tanks 1a, 1b, 1c.
  • the coating B which is composed of the individual layers B1, B2, B3, contains as essential components metallic chromium (chrome metal) and chromium oxides (CrOx), the composition of the individual layers B1, B2, B3 in relation to their respective weight fraction of Chromium metal and chromium oxide are different due to the different current densities j 1 , j 2 , j 3 in the electrolysis tanks 1a, 1b, 1c. Furthermore, a possibly different temperature of the electrolyte solution in the electrolysis tanks 1a, 1b, 1c also contributes to the fact that the individual layers differ in terms of their composition since (as above with reference to FIG Figure 5 explained) at lower temperatures of 40 ° C or less, the formation of chromium oxide is promoted.
  • metallic chromium chrome metal
  • CrOx chromium oxides
  • a high current density j 3 (which is higher than the current density j 1 , j 2 in the preceding electrolysis tanks) and, at the same time, a low temperature of the electrolyte solution of 40 ° C. are preferably used in the last electrolysis tank 1c or less set.
  • a current density j3 is set which lies in regime III, in which an increased chromium oxide content in of the coating is produced, which is preferably more than 40% by weight and particularly preferably more than 50% by weight.
  • the current densities j 1 , j 2 present in the first two electrolysis tanks 1a, 1b are therefore each in Regime II, in which there is a linear relationship between the current density and the electrolytically deposited amount of chromium (or the deposited weight support of chromium).
  • the current density j 1 of the first electrolysis tank 1 a is expediently selected such that it is close to the first current density threshold, which delimits the regime I (in which no chromium deposition takes place yet) from the regime II.
  • a chrome metal-chromium oxide coating (layer B1) is deposited on the surface of the metal strip M with a higher chromium oxide content than at higher current densities within the regime II.
  • the layer deposited in the first electrolysis tank 1a therefore has B1 has a higher chromium oxide content in comparison to the layer B2 deposited in the second electrolysis tank 1b.
  • a current density j 3 is preferably set in the last electrolysis tank 1a, which lies above the second current density threshold, which delimits regime II from regime III.
  • the current density j 3 of the last electrolysis tank 1c is therefore in regime III, in which the chromium-metal-chromium oxide coating is partially decomposed and a significantly higher proportion of chromium oxide is deposited than in the current densities in regime II last electrolysis tank 1c deposited layer B3 has a high chromium oxide content which is higher than the chromium oxide content in layers B1 and B2.
  • the metal strip M provided with the coating B is rinsed, dried and oiled (for example with DOS).
  • the metal strip M electrolytically coated with the coating B can then be provided with an organic coating on the surface of the coating B.
  • the organic coating can be, for example, an organic lacquer or polymer films made from thermoplastic polymers such as PET, PP, PE or mixtures thereof.
  • the organic overlay can be applied either in a "coil coating" process or in a board process, the coated metal strip in the board process first being divided into boards which are then coated with an organic lacquer or coated with a polymer film .
  • FIG 2 shows a second embodiment of a strip coating system with eight electrolysis tanks 1a-1h arranged one behind the other in the strip running direction v.
  • the electrolysis tanks 1a-1h are grouped into three groups, namely a front group with the first two electrolysis tanks 1a, 1b, a middle group with the downstream electrolysis tanks 1c-1f and a rear group with the last two electrolysis tanks 1g and 1h.
  • a temperature of the electrolytic solution of 40 ° C. or less is present in the rear group of the electrolysis tanks 1g and 1h.
  • the front group with the two first electrolysis tanks 1a, 1b and the middle group with the electrolysis tanks 1c-1f either the same or at least approximately the same temperature or a higher temperature can be present.
  • Current densities j 1 , j 2 , j 3 are preferably present in the groups of electrolysis tanks, with a low current density j 1 in the front group of electrolysis tanks 1 a -1f and an average current density j 2 in the middle group of electrolysis tanks 1 c- 1 f and in the rear group of electrolysis tanks 1g, 1h there is a high current density j 3 , where j 1 ⁇ j 2 ⁇ j 3 and the low current density j 1 > 20 A / dm 2 .
  • Table 2 shows examples of suitable current densities j 1 , j 2 , j 3 in the individual electrolysis tanks 1a to 1h at different belt speeds, with a current density j 1 in each of the electrolysis tanks 1a, 1b of the front group in the electrolysis tanks 1c to 1f of the middle group each a current density j 2 and in the electrolysis tanks 1g, 1h of the rear group a current density j 3 is set, where j 1 ⁇ j 2 ⁇ j 3 .
  • layers B1, B2, B3 have different compositions, layer B1 containing a higher chromium oxide content than the second Layer B2 and the third layer B3 contains a higher chromium oxide content than the two layers B1 and B2.
  • the total electrolysis time in which the metal strip M is in electrolytically effective contact with the electrolyte solution E is in the exemplary embodiment of Figure 2 across all electrolysis tanks 1a-1h preferably in less than 16 seconds and in particular between 4 and 16 seconds.
  • the coatings B preferably have a total chromium weight support of at least 40 mg / m 2 and particularly preferably from 70 mg / m 2 to 180 mg / m 2 .
  • Coating B expediently has a total chromium oxide content with a chromium oxide bond weight of chromium bound of at least 3 mg chromium per m 2 and in particular 3 to 15 mg / m 2 .
  • the weight of the chromium bound as chromium oxide, averaged over the entire coating B coating, is preferably at least 7 mg of chromium per m 2 .
  • Good adhesion of organic paints or thermoplastic polymer materials to the surface of coating B can be achieved with chromium oxide weights of up to approximately 15 mg / m 2 .
  • a preferred range for the weight of the chromium oxide in the coating B is therefore between 5 and 15 mg / m 2 .
  • Table 3 shows an example of the composition of an electrolyte solution which contains a Cr (III) salt (Cr 2 (SO 4 ) 3 ) and has been used for coating experiments in a laboratory apparatus for the electrolytic coating of a metal strip.
  • the parameters of the electrolyte solution used can be found in Table 4.
  • the Cr (III) salt used as part of the electrolyte solution should be as free as possible from organic residues.
  • the Cr (III) salts can be prepared on an industrial scale by reduction from Cr (VI) salts.
  • a less noble metal than chromium (variant 1), or alternatively an organic component (variant 2) is preferably used as the reducing agent.
  • the pH of the electrolyte solution was adjusted by adding sulfuric acid and then filling up with deionized water.
  • a steel sheet already coated with a chromium / chromium oxide layer was used as the substrate for the coating experiments.
  • This material was electrolytically coated with a chromium (III) electrolyte at 55 ° C. and Table 5 below describes the already existing coating of the steel sheet with chromium metal and chromium oxide. It can be seen that mainly chromium metal and only a little chromium oxide was formed.
  • the chromium metal determination was carried out according to EURO Norm EN 10202 (Cr-metal photometric (euro-norm) step 2: 120 ml NaCO 3 and 15 mA / plane; successfull dissolution visible by potential step, oxidation with 10 ml 6% H 2 O 2 , photometric @ 370 nm).
  • the chromium oxide determination was also carried out according to the EURO standard EN 10202 (Cr-oxides photometric: (euro-norm) step 1: 40 ml NaOH (330g / L), reaction at 90 ° C for 10 minutes, oxidation with 10 ml 6% H 2 O 2 , photometric @ 370 nm).
  • the substrate was degreased (2.5 A / dm 2 connected cathodically, 30 sec., 70 ° C in sodium hydroxide solution) and then rinsed with deionized water.
  • the subsequent pickling process was dispensed with due to the already existing metallic coating.
  • Tables 6 and 7 summarize the parameters and the results of the coating tests.
  • a large-scale coating of a steel strip with a belt speed of 100 m / min was simulated. At this speed, the selected current density of 60 A / dm 2, which is kept constant during the test, is in Regime III (see Table 2) and thus (at least at the lower temperatures) mainly produces chromium oxide.
  • Regime III see Table 2
  • both the temperatures of the electrolyte solutions and the holding times (electrolysis time) were varied in Regime III.
  • the underside of the substrate was coated in each case.
  • the electrolysis time in the relevant regime III is given in Table 5 with "time (s) segment 1".
  • the electrolysis times in the respective regime were less than 2 seconds. As the duration of the electrolysis increased, a higher oxide occupancy was observed in the laboratory tests. However, short electrolysis times of less than 2 seconds are large in terms of efficiency Process control to be preferred since high belt speeds of preferably more than 100 m / min are used here.

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EP3733932A1 (fr) * 2019-04-09 2020-11-04 ThyssenKrupp Rasselstein GmbH Procédé de fabrication d'une bande métallique revêtue d'un revêtement de chrome et d'oxyde de chrome à base d'une solution électrolytique avec un composé à base de chrome trivalent et système d'électrolyse permettant la mise en oeuvre dudit procédé

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DE102018132074A1 (de) 2018-12-13 2020-06-18 thysenkrupp AG Verfahren zur Herstellung eines mit einer Beschichtung aus Chrom und Chromoxid beschichteten Metallbands auf Basis einer Elektrolytlösung mit einer dreiwertigen Chromverbindung
WO2022138005A1 (fr) * 2020-12-21 2022-06-30 Ｊｆｅスチール株式会社 Feuille d'acier traitée en surface et son procédé de production
KR20230093037A (ko) * 2020-12-21 2023-06-26 제이에프이 스틸 가부시키가이샤 표면 처리 강판 및 그 제조 방법
WO2022138006A1 (fr) * 2020-12-21 2022-06-30 Ｊｆｅスチール株式会社 Feuille d'acier traitée en surface et son procédé de production
MX2023007454A (es) * 2020-12-21 2023-07-04 Jfe Steel Corp Lamina de acero tratada en la superficie y metodo para producir la misma.
KR20240146032A (ko) * 2022-04-08 2024-10-07 제이에프이 스틸 가부시키가이샤 표면 처리 강판 및 그 제조 방법
WO2023195252A1 (fr) * 2022-04-08 2023-10-12 Ｊｆｅスチール株式会社 Tôle d'acier traitée en surface et son procédé de production
WO2023195251A1 (fr) * 2022-04-08 2023-10-12 Ｊｆｅスチール株式会社 Tôle d'acier traitée en surface et son procédé de production
KR20240141805A (ko) * 2022-04-08 2024-09-27 제이에프이 스틸 가부시키가이샤 표면 처리 강판 및 그 제조 방법

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EP3733932A1 (fr) * 2019-04-09 2020-11-04 ThyssenKrupp Rasselstein GmbH Procédé de fabrication d'une bande métallique revêtue d'un revêtement de chrome et d'oxyde de chrome à base d'une solution électrolytique avec un composé à base de chrome trivalent et système d'électrolyse permettant la mise en oeuvre dudit procédé

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CN111321431A (zh) 2020-06-23
US20200190679A1 (en) 2020-06-18
KR102268789B1 (ko) 2021-06-28
ES2898373T3 (es) 2022-03-07
DE102018132075A1 (de) 2020-06-18
US11274373B2 (en) 2022-03-15
KR20200074031A (ko) 2020-06-24
EP3666931B1 (fr) 2021-10-20
CN111321431B (zh) 2024-09-10
BR102019025858A2 (pt) 2020-06-23

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