EP3666931B1 - Verfahren zur herstellung eines mit einer beschichtung aus chrom und chromoxid beschichteten metallbands auf basis einer elektrolytlösung mit einer dreiwertigen chromverbindung - Google Patents
Verfahren zur herstellung eines mit einer beschichtung aus chrom und chromoxid beschichteten metallbands auf basis einer elektrolytlösung mit einer dreiwertigen chromverbindung Download PDFInfo
- Publication number
- EP3666931B1 EP3666931B1 EP19206950.8A EP19206950A EP3666931B1 EP 3666931 B1 EP3666931 B1 EP 3666931B1 EP 19206950 A EP19206950 A EP 19206950A EP 3666931 B1 EP3666931 B1 EP 3666931B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrolysis
- chromium
- electrolyte solution
- chromium oxide
- coating
- 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.)
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Links
- 238000000576 coating method Methods 0.000 title claims description 125
- 239000011248 coating agent Substances 0.000 title claims description 107
- 229910000423 chromium oxide Inorganic materials 0.000 title claims description 106
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 title claims description 103
- 229910052751 metal Inorganic materials 0.000 title claims description 75
- 239000002184 metal Substances 0.000 title claims description 75
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 68
- 239000011651 chromium Substances 0.000 title claims description 59
- 229910052804 chromium Inorganic materials 0.000 title claims description 45
- 238000000034 method Methods 0.000 title claims description 43
- 239000003792 electrolyte Substances 0.000 title description 14
- 238000005868 electrolysis reaction Methods 0.000 claims description 272
- 239000008151 electrolyte solution Substances 0.000 claims description 92
- 239000000203 mixture Substances 0.000 claims description 18
- 150000001845 chromium compounds Chemical class 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 7
- -1 alkali metal carboxylate Chemical class 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052936 alkali metal sulfate Inorganic materials 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000004280 Sodium formate Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 239000000872 buffer Substances 0.000 claims description 2
- 239000006172 buffering agent Substances 0.000 claims description 2
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 claims description 2
- 150000004675 formic acid derivatives Chemical class 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims description 2
- 235000019254 sodium formate Nutrition 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims 1
- 239000001120 potassium sulphate Substances 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- 229940021013 electrolyte solution Drugs 0.000 description 74
- 239000010410 layer Substances 0.000 description 49
- 229910000831 Steel Inorganic materials 0.000 description 23
- 239000010959 steel Substances 0.000 description 23
- 230000007797 corrosion Effects 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 13
- 230000008021 deposition Effects 0.000 description 11
- 239000000758 substrate Substances 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000004922 lacquer Substances 0.000 description 6
- 229920006254 polymer film Polymers 0.000 description 6
- 239000005029 tin-free steel Substances 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 5
- 238000009533 lab test Methods 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000005028 tinplate Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical class [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- GVEHJMMRQRRJPM-UHFFFAOYSA-N chromium(2+);methanidylidynechromium Chemical compound [Cr+2].[Cr]#[C-].[Cr]#[C-] GVEHJMMRQRRJPM-UHFFFAOYSA-N 0.000 description 1
- KZYOZXGUWRHMHN-UHFFFAOYSA-N chromium(3+) oxygen(2-) Chemical compound [O-2].[Cr+3].[O-2].[Cr+3] KZYOZXGUWRHMHN-UHFFFAOYSA-N 0.000 description 1
- DSHWASKZZBZKOE-UHFFFAOYSA-K chromium(3+);hydroxide;sulfate Chemical compound [OH-].[Cr+3].[O-]S([O-])(=O)=O DSHWASKZZBZKOE-UHFFFAOYSA-K 0.000 description 1
- OGDYVWQEAVKKDI-UHFFFAOYSA-N chromium(3+);oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Cr+3].[Cr+3] OGDYVWQEAVKKDI-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 229910000356 chromium(III) sulfate Inorganic materials 0.000 description 1
- 235000015217 chromium(III) sulphate Nutrition 0.000 description 1
- 239000011696 chromium(III) sulphate Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
Images
Classifications
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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
- 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
- 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
- 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.
- tin-free steel sheet steel sheets which are electrolytically coated with a coating of chromium and chromium oxide are known from the prior art, which are referred to as tin-free steel sheet ("Tin Free Steel", TFS) or as “Electrolytic Chromium Coated Steel (ECCS)" and a Represent an alternative to tinplate.
- TFS Tin Free Steel
- ECCS Electrolytic Chromium Coated Steel
- tin-free steel sheets are particularly characterized by good adhesion for paints or organic protective coatings (such as, for example, 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, e.g. in deep-drawing and ironing processes.
- electrolytic coating processes are known from the prior art, with which the coating is applied in a strip coating system to a strip-shaped steel sheet using an electrolyte containing chromium VI.
- these coating processes due to the properties of the chromium VI-containing electrolytes used in the electrolysis process, which are hazardous to the environment and health, these coating processes have considerable disadvantages and will have to be replaced by alternative coating processes in the foreseeable future, as 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 sheet (uncoated steel sheet) or a tinplate (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 electrolyte solution which contains a trivalent chromium compound (Cr-III), with an anode is provided that prevents or at least reduces the oxidation of chromium (III) ions to chromium (VI) ions and hydrogen bubbles that arise during the electrolytic deposition of the coating on the surface of the substrate are removed.
- Cr-CrOx chrome metal-chromium oxide
- Cr-III trivalent chromium compound
- the deposition reaction and the surface properties of the electrolytically deposited coating depend on the temperature of the electrolyte solution and that temperatures of the electrolyte solution between 30 ° C and 70 ° C are suitable for producing coatings with a good surface appearance.
- a preferred temperature range between 40 ° C. and 60 ° C. has been recognized as advantageous with regard to an efficient deposition reaction because the electrolyte solution has good conductivity at these temperatures.
- a method for the electrolytic coating of a strip-shaped steel sheet with a chromium metal / chromium oxide (Cr-CrOx) layer in a strip coating system in which the steel sheet, connected as a cathode, is passed through an electrolyte solution at high strip speeds of more than 100 m / min, which contains a trivalent chromium compound (Cr-III).
- composition of the coating which, depending on the components still contained in the electrolyte solution in addition to the trivalent chromium compound (Cr-III), can also contain chromium sulfate and chromium carbide in addition to the constituents chromium metal and chromium oxide, depends to a large extent on the current densities of the electrolysis depends, which are set at the anodes during the electrolytic deposition process in the electrolysis tanks in which the electrolyte solution is contained.
- the coating contains a higher one Chromium oxide content, which makes up between 1 ⁇ 4 and 1/3 of the total weight of the coating in the area of higher current densities.
- the values of the current density thresholds that delimit the areas (regime I to III) depend on the belt speed with which the steel sheet is moved through the electrolyte solution.
- Another method for the electrolytic coating of a black sheet with a chromium metal / chromium oxide (Cr-CrOx) layer made of an electrolyte with a trivalent chromium compound is from EP 3 378 973-A1 known, in which the black plate connected as cathode is passed at a speed of at least 50 m / min in a coating line through the electrolyte, which has a temperature between 30 and 70 ° C and preferably at least 40 ° C.
- the object of the present invention is to provide a method that is as efficient as possible and can be carried out on an industrial scale in a coil coating system for producing a metal strip coated with a coating of chromium and chromium oxide based on an electrolyte solution with a trivalent chromium compound, the coating having the highest possible proportion of chromium oxide is intended to achieve adequate corrosion resistance of the coated metal strip and a good adhesive base for organic coatings, such as paints or polymer films made of PET or PP.
- a coating containing chromium metal and chromium oxide is applied electrolytically from an electrolyte solution containing a trivalent chromium compound to a metal strip, in particular a steel strip, by bringing the metal strip into contact with the electrolyte solution connected as a cathode , the metal strip successively at a predetermined strip speed in a strip running direction at least through a first electrolysis tank (1a) or a front group of electrolysis tanks (1a, 1b) and through a last electrolysis tank (1c) or a rear group of electrolysis tanks (1g) as seen in the strip running direction , 1h), the temperature of the electrolyte solution in the first electrolysis tank (1a) or the front group of electrolysis tanks (1a, 1b) averaged over the volume of the electrolysis tank being greater than the average temperature of the electrolyte solution in the last electrolysis tank (1c) or the rear group of E electrolysis tanks (1g, 1h) and in the last electrolysis tank seen in the direction
- chromium oxide all oxide forms of chromium (CrOx), including chromium hydroxides, in particular chromium (III) hydroxide and chromium (III) oxide hydrate, as well as mixtures thereof are meant.
- the electrolysis time in which the metal strip is in effective electrolytic contact with the electrolyte solution is expediently less than 2 seconds in each of the electrolysis tanks, so that the metal strip moves at a constant belt speed through the several electrolysis tanks arranged one behind the other in the direction of belt travel, which are expediently designed in the same way are, can be guided.
- 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 effective electrolytic 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 electrolyte solution in the first electrolysis tank or in the front group of electrolysis tanks can be higher than in the last electrolysis 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 ° C and in particular between 53 ° C and 70 ° C, since in this temperature range a more efficient deposition of chromium, in particular in the form of chromium metal , can be observed.
- a coating can be deposited on the surface of the metal strip, at least one lower and one upper Layer comprises, wherein the lower layer is deposited 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 and the lower layer has a low proportion of chromium oxide and the upper layer a higher one Has 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 is preferably between 20 ° C and less than 40 ° C and particularly preferably between 25 ° C and 38 ° C. Due to the exothermic deposition process, the electrolyte solution in the electrolysis tanks must be cooled in order to maintain the preferred temperatures. This is made more difficult by the fact that the circulation systems of the electrolysis tanks are usually coupled. Therefore, for reasons of apparatus, it can be expedient to maintain the same temperature in each case in the electrolysis tanks in order to avoid different settings that are expensive in terms of apparatus.
- 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 electrolyte solution in the second electrolysis tank or the rear group of electrolysis tanks.
- the metal strip is first guided 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.
- composition of the coating deposited electrolytically on the metal strip depends not only on the temperature of the electrolyte solution but also on the current density of the electrolysis process. It has been shown that at higher current densities, which are in the range of regime III, where (partial) decomposition of the applied coating already takes place, a higher proportion of chromium oxide is generated in the coating, compared to the lower current densities in regime II, where a linear relationship between the deposited weight of the chromium and the current density can be observed.
- a low current density j 1 or j 2 should be applied in the first electrolysis tank or in the front group of electrolysis tanks and, if necessary, in the second electrolysis tank following in the direction of strip travel or in the middle group of electrolysis tanks, and in the last electrolysis tank or in In the rear group of electrolysis tanks, a high current density j 3 must be provided in regime III, where j 1 and j 2 are less than j 3 and, for example, at a belt speed of 100 m / min, the low current densities j 1 and j 2 are each greater than 20 A / dm 2 (and thus are above the first current density threshold of approx.
- the current densities j 1 , j 2 and j 3 are increased, so that for example 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 that a lower current density is present in the first electrolysis tank or in the front group of electrolysis tanks compared to the second electrolysis tank following in the direction of belt travel or in the middle group of electrolysis tanks, so that the ratio 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 in terms of their proportion of chromium metal and chromium oxide, the lower layer facing the metal strip having an average weight proportion of chromium oxide, which is in particular in the range of 10% to 15%, the middle layer has a low percentage by weight of chromium oxide, which is in particular in the range from 2% to 10%, and the upper layer has a high percentage by weight of chromium oxide, which is in particular more than 30%, preferably at is more than 50%.
- the coating having the proportion of chromium oxide required for adequate corrosion resistance of at least 5 mg / m 2 , preferably more than 7 mg / m 2 .
- the total weight of the chromium oxide does not exceed 15 mg / m 2 , since with higher weight of the chromium oxide, reduced adhesion of organic coatings made of lacquers or thermoplastic polymer materials is observed.
- a preferred range for the weight of the chromium oxide is between 5 and 15 mg / m 2 .
- a certain weight proportion of the total amount of the deposited coating which is approx. 9 to 15%, is made up of chromium oxide Chromium oxide crystals develop on the surface of the metal strip already 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 nucleus for the growth of further oxide crystals, which is why this increases the efficiency of the deposition of chromium oxide or the proportion of chromium oxide in the total application of the coating in the last electrolysis tank or in the rear group of electrolysis tanks increases.
- a sufficiently high level of chromium oxide of preferably more than 5 mg / m 2 on the surface of the Metal bands are produced.
- the proportion of chromium oxide generated 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 due to the higher oxygen content in the coating compared to electrolytic deposition with higher current densities (and consequently a lower oxide content ) a denser coating, which leads to improved corrosion resistance.
- a current density of at least 20 A / dm 2 is required 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 represents the first current density threshold value at a belt speed of approx. 100 m / min, which corresponds to regime I (no chromium deposition) of regime II (chromium deposition with a linear relationship between current density and the chromium weight of the deposited coating ) delimits.
- the current densities (j 1 , j 2 , j 3 ) in the electrolysis tanks are each adapted to the belt speed, with at least an essentially 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 smaller 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, which is preferably more than 8%, in particular between 8 and 15%, directly on the surface of the metal strip particularly preferably more than 10% by weight.
- At least one anode pair with two opposing anodes is expediently arranged in each electrolysis tank, the metal strip running through between the opposing anodes of an anode pair. This allows an even current density distribution around the Metal band can be achieved.
- 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 belt speed of the metal belt is expediently chosen so that the electrolysis time (t E ) in which the metal belt is in effective electrolytic 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 of at least 40 mg / m 2 and in particular 70 mg / m 2 to 180 mg / m 2 to achieve adequate corrosion resistance of the coated metal strip.
- the proportion by weight of chromium oxide contained in the coating in relation to 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 the 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 of 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 electrolyte 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 at least 10 g / l and preferably more than 15 g / l and is in particular 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 electrolyte solution can be an alkali metal sulfate, preferably potassium or sodium sulfate.
- the electrolyte solution is preferably free from halides, in particular free from chloride and bromide ions and free from a buffering agent and in particular free from 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.
- an organic coating in particular a lacquer or a thermoplastic, for example a polymer film made of PET, PE, PP or a mixture thereof, can be applied to the surface of the coating made of chrome metal and chrome oxide in order to provide additional protection against corrosion and to form 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 next to one another 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 one after the other.
- the metal strip M is pulled through the electrolysis tanks 1a-1c by a transport device (not shown here) in a strip running direction v at a predetermined strip speed.
- Current rollers S are arranged above the electrolysis tanks 1a-1c, via which the metal strip M is connected as a cathode.
- In each electrolysis tank there is also a deflection roller U, around which the metal strip M is guided and is thereby directed into and out of the electrolysis tank.
- each electrolysis tank 1a-1c at least one pair of anodes AP is arranged below the liquid level of the electrolyte solution E.
- two pairs of anodes AP arranged one behind the other in the direction of travel of the strip are provided in each electrolysis tank 1a-1c.
- the metal strip M is passed between the opposing anodes of an anode pair AP.
- two pairs of anodes AP are arranged in each electrolysis tank 1a, 1b, 1c in such a way that the metal strip M is passed through these pairs of anodes AP one after the other.
- the last pair of anodes APc in the downstream direction of the last electrolysis tank 1c seen in the direction of travel v of the strip has a shorter length than the other pairs of anodes AP. As a result, a higher current density can be generated with this last pair of anodes APc when an electric current of the same level 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 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 into each of the electrolysis tanks 1a-1c arranged one behind the other in the strip running direction v.
- the electrolyte 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 can 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.degree. 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 upstream electrolysis tanks 1a and 1b.
- the temperature of the electrolyte 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 is preferably between 50.degree. C. and 75.degree. C. and in particular 55.degree.
- the lower temperature of the electrolyte solution E promotes the deposition of a chromium / chromium oxide layer with a higher proportion of chromium oxide in the last electrolysis tank 1c.
- the metal belt M connected as a cathode and guided through the electrolysis tanks 1a-1c is in electrolytically effective contact with the electrolyte solution E during an electrolysis period t E.
- the electrolysis period is in each of the electrolysis tanks 1a, 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 in particular between 0.6 seconds and 1.8 seconds.
- the total electrolysis time in which the metal strip M over all electrolysis tanks 1a-1c is in electrolytically effective contact with the electrolyte solution E away, is accordingly between 1.8 and 5.4 seconds.
- the anode pairs AP arranged in the electrolysis tanks 1a-1c can be supplied with electrical direct current in such a way that the same current density is present in each of the electrolysis tanks 1a, 1b, 1c.
- a coating B with a plurality of layers B1, B2, B3 of different composition on the metal strip M it is also possible to set different current densities in the electrolysis tanks 1a, 1b, 1c.
- a low current density j 1 can be set in the first electrolysis tank 1a upstream as seen in the strip running direction v, an average current density j 2 in the second electrolysis tank 1b following in the strip running direction and a high current density j 3 in the last electrolysis tank 1c as seen in the strip running direction so that the relation j 1 ⁇ j 2 ⁇ j 3 applies and the low current density is j 1 > 20 A / dm 2 .
- each electrolytically applied layer B1, B2, B3 has a different composition, which differs in particular through the proportion of chromium oxide.
- FIG 3 a schematic sectional view of a metal strip M which is electrolytically coated on one side using the method according to the invention is shown.
- a coating B which is composed of the individual layers B1, B2, B3, is applied to one side of the metal strip M.
- 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 metallic chromium (chromium metal) and chromium oxides (CrOx) as essential components, the composition of the individual layers B1, B2, B3 in relation to their respective weight fraction of Chromium metal and chromium oxide due to the different current densities j 1 , j 2 , j 3 in the electrolysis tanks 1a, 1b, 1c is different. Furthermore, a possibly different temperature of the electrolyte solution in the electrolysis tanks 1a, 1b, 1c contribute to the fact that the individual layers differ in terms of their composition, since (as above based on Figure 5 explained) at lower temperatures of 40 ° C or less, the formation of chromium oxide is promoted.
- 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. is preferred in the last electrolysis tank 1c or less.
- a current density j3 is set which is in regime III, in which an increased chromium oxide content is generated in the coating, which is preferably more than 40% by weight and particularly preferably more than 50% by weight.
- the current density j 1 of the first electrolysis tank 1a is expediently selected so that it is close to the first current density threshold which delimits regime I (in which no chromium is yet deposited) from regime II.
- a chromium 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 regime II B1 has a higher chromium oxide content than the layer B2 deposited in the second electrolysis tank 1b.
- a current density j 3 is preferably set which is 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 with the current densities in regime II.
- the im Layer B3 deposited in the last electrolysis tank 1c 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 layer 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 coating can be applied either in a "coil coating" process or in a panel process, the coated metal strip being first divided into panels in the panel process, which are then coated with an organic lacquer or coated with a polymer film will.
- FIG 2 shows a second embodiment of a coil coating system with eight electrolysis tanks 1a-1h arranged one behind the other in the direction of travel v of the coil.
- 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 subsequent electrolysis tanks 1c-1f in the direction of belt travel and a rear group with the last two electrolysis tanks 1g and 1h.
- the temperature of the electrolyte solution is 40 ° C. or less.
- either the same or at least approximately the same temperature or also a higher temperature can be present.
- higher temperatures of more than 50 ° C. and in particular of approx. 55 ° C. are preferred in the electrolysis tanks 1a, 1b of the front group and the electrolysis tanks 1c-1f of the middle group.
- the groups of electrolysis tanks there are preferably different current densities j 1 , j 2 , j 3 , with a low current density j 1 in the front group of electrolysis tanks 1a, 1b and an average current density j 2 in the middle group of electrolysis tanks 1c-1f 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 is 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 in the front group and a current density j 1 in the electrolysis tanks 1c to 1f of the middle group each have a current density j 2 and a current density j 3 is set in each of the electrolysis tanks 1g, 1h of the rear group, where j 1 ⁇ j 2 ⁇ j 3 .
- a first layer B1 containing chromium metal and chromium oxide is electrolytically applied to the metal strip, in the second group of electrolysis tanks 1c-1f a second layer B2 and in the rear group of electrolysis tanks 1g, 1h a third layer B3 M applied.
- Layers B1, B2, B3 have different compositions due to the different current densities j 1 , j 2 , j 3 and possibly different temperatures in the groups of electrolysis tanks arranged one behind the other, with layer B1 containing a higher chromium oxide content than the second Layer B2 and the third layer B3 contain a higher proportion of chromium oxide than the two layers B1 and B2.
- Coating B applied to the surface of the metal strip M thus has essentially the same composition and structure as in FIG Figure 3 shown.
- the entire electrolysis time in which the metal strip M is in electrolytically effective contact with the electrolyte solution E is in the embodiment of FIG Figure 2 across all electrolysis tanks 1a-1h, preferably for less than 16 seconds and in particular between 4 and 16 seconds.
- the coatings B preferably have a total weight of the chromium of at least 40 mg / m 2 and particularly preferably from 70 mg / m 2 to 180 mg / m 2 .
- the coating B expediently has a total of chromium oxide with a weight add-on of the chromium bound as chromium oxide of at least 3 mg chromium per m 2 and in particular from 3 to 15 mg / m 2 .
- the amount by weight of the chromium bound as chromium oxide, averaged over the entire amount of coating B, is preferably at least 7 mg of chromium per m 2 .
- Good adhesion of organic lacquers or thermoplastic polymer materials on the surface of the coating B can be achieved with weight of the chromium oxide of up to approx. 15 mg / m 2 .
- a preferred range for the weight of the chromium oxide in 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 tests in 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 a component of the electrolyte solution should be as free of organic residues as possible.
- the preparation of the Cr (III) salts can be carried out on an industrial scale by means of reduction from Cr (VI) salts be performed.
- the reducing agent used is preferably a less noble metal than chromium (variant 1), or alternatively an organic component (variant 2).
- the pH of the electrolyte solution was adjusted by adding sulfuric acid followed by topping up with deionized water.
- a steel sheet already coated with a chromium / chromium oxide layer was used as the substrate for the coating tests.
- This material was electrolytically coated at 55 ° C. with a chromium (III) electrolyte and Table 5 below describes the 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 the 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 to the cathode, 30 seconds, 70 ° C. in sodium hydroxide solution) and then rinsed with deionized water.
- the subsequent pickling process was dispensed with due to the existing metallic coating.
- Tables 6 and 7 summarize the parameters and the results of the coating tests.
- a large-scale coating of a steel belt with a belt speed of 100 m / min was simulated. At this speed, the selected current density of 60 A / dm 2, which was kept constant during the test, is in regime III (see Table 2) and thus mainly generates chromium oxide (at least at the lower temperatures).
- 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 duration of the electrolysis in the relevant regime III is given in Table 5 as “time (s) segment 1”.
- the electrolysis times in the respective regime were less than 2 seconds. With increasing electrolysis time, a higher oxide coating was observed in the laboratory tests. However, short electrolysis times of less than 2 seconds are to be preferred in terms of efficiency in a large-scale process, since high belt speeds of preferably more than 100 m / min are used here.
- Temperature TCCT tank [° C] pH value VA08 Conductance VA08 [mS / cm] pH value (55 ° C) Conductivity 55 ° C [mS / cm] Chromium concentration electrolyte (g / L) Iron concentration electrolyte (mg / L) Chloride concentration electrolyte (mg / l) Electrolyte surface explosion 1st cycle at ⁇ 55 ° C ( ⁇ C / cm 2 ) Electrolyte surface explosion 2nd cycle at ⁇ 55 ° C ( ⁇ C / cm 2 ) 13th 02/28/2017 55 2.4 88.5 2.3 158.3 22.6 270 182 348.8 327.8 Serial no.
- chromium metal OS (mg / m 2 ) ⁇ chromium metal US (mg / m 2 ) ⁇ chromium oxide OS (mg / m 2 ) ⁇ chromium oxide US (mg / m 2 ) 11 63 111 3 1
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