EP3538688B1 - Method for electroplating an uncoated steel strip with a plating layer - Google Patents
Method for electroplating an uncoated steel strip with a plating layer Download PDFInfo
- Publication number
- EP3538688B1 EP3538688B1 EP17797316.1A EP17797316A EP3538688B1 EP 3538688 B1 EP3538688 B1 EP 3538688B1 EP 17797316 A EP17797316 A EP 17797316A EP 3538688 B1 EP3538688 B1 EP 3538688B1
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- EP
- European Patent Office
- Prior art keywords
- plating
- electrolyte
- strip
- current
- chromium
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- 238000007747 plating Methods 0.000 title claims description 89
- 229910000831 Steel Inorganic materials 0.000 title claims description 43
- 239000010959 steel Substances 0.000 title claims description 43
- 238000000034 method Methods 0.000 title claims description 42
- 238000009713 electroplating Methods 0.000 title claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 55
- 230000008569 process Effects 0.000 claims description 22
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 17
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 claims description 8
- 238000004210 cathodic protection Methods 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 6
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 6
- 239000001117 sulphuric acid Substances 0.000 claims description 6
- 235000011149 sulphuric acid Nutrition 0.000 claims description 6
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000005554 pickling Methods 0.000 claims description 5
- 229910003470 tongbaite Inorganic materials 0.000 claims description 5
- 239000011696 chromium(III) sulphate Substances 0.000 claims description 4
- 235000015217 chromium(III) sulphate Nutrition 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 239000004280 Sodium formate Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000000356 contaminant Substances 0.000 claims description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019254 sodium formate Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims description 2
- 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 claims 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims 2
- 239000001120 potassium sulphate Substances 0.000 claims 2
- 235000011151 potassium sulphates Nutrition 0.000 claims 2
- 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 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 239000011651 chromium Substances 0.000 description 21
- 229910052804 chromium Inorganic materials 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- 230000008021 deposition Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000005028 tinplate Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910019923 CrOx Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910005382 FeSn Inorganic materials 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- QOWZHEWZFLTYQP-UHFFFAOYSA-K chromium(3+);triformate Chemical compound [Cr+3].[O-]C=O.[O-]C=O.[O-]C=O QOWZHEWZFLTYQP-UHFFFAOYSA-K 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NNIPDXPTJYIMKW-UHFFFAOYSA-N iron tin Chemical compound [Fe].[Sn] NNIPDXPTJYIMKW-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
-
- 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
- C25D7/0642—Anodes
-
- 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
- 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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
-
- 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
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
- C25D9/10—Electrolytic coating other than with metals with inorganic materials by cathodic processes on iron or steel
Definitions
- This invention relates to a method for electroplating an uncoated steel strip with a plating layer and an improvement thereof.
- a cold-rolled steel strip is provided which is usually annealed after cold-rolling to soften the steel by recrystallisation annealing or recovery annealing. After the annealing and before plating the steel strip is first cleaned for removing oil and other surface contaminants.
- an alkaline cleaner is used for this purpose, wherein steel is electrochemically passive, i.e. the steel strip surface is covered with a stable and protective oxide film and therefore the steel will not dissolve in the alkaline cleaner.
- the alkaline cleaner is a complex mixture of various ingredients.
- the main component is caustic soda for providing alkalinity, conductivity, and saponification.
- Other common components are sodium metasilicate, sodium carbonate, phosphates, borates, and surfactants.
- the steel strip is pickled in a sulphuric or hydrochloric acid solution for removing the oxide film.
- a sulphuric or hydrochloric acid solution for removing the oxide film.
- the steel strip is always rinsed with deionised water to prevent contamination of the solution used for the next treatment step with solution of the preceding treatment step. Consequently the steel strip is thoroughly rinsed after the pickling step.
- a fresh thin oxide layer is formed instantly on the bare steel surface.
- the process used in electroplating is called electrodeposition.
- the part to be plated (the steel strip) is the cathode of the circuit.
- the anode of the circuit may be made of the metal to be plated on the part (dissolving anode, such as those used in conventional tinplating) or a dimensionally stable anode (which does not dissolve during plating). Both components are immersed in a solution called an electrolyte. At the cathode, the metal ions in the electrolyte solution are reduced at the interface between the solution and the cathode, such that they deposit onto the cathode.
- electrolytes are acidic solutions. As a consequence the oxide layer that was formed after the pickling step will dissolve rapidly. Bare steel without any oxide film is prone to corrosion. Corrosion means that iron from the steel substrate is oxidised to Fe 2+ , where the liberated electrons are consumed by the reduction of hydrogen ions or oxygen gas that is dissolved in the electrolyte. 2H + + 2e - ⁇ H 2 (g) O 2 (g) + 4H + + 4e - ⁇ 2H 2 O The consequence is that the electrolyte becomes enriched in Fe 2+ .
- these Fe 2+ -ions are subsequently reduced in the following electroplating step to Fe and this Fe is deposited onto the substrate along with the metal that is intended to be plated onto the substrate.
- the codeposited iron adversely affects the properties of the plated layer, particularly the corrosion performance.
- One or more of the objects is reached by a method for electroplating an uncoated steel strip with a plating layer from a trivalent Cr-electrolyte, wherein the uncoated strip is subjected to a cleaning and pickling step prior to the plating process to remove oxides and any other contaminants present on the surface or surfaces of the strip, and wherein the strip is subsequently subjected to a plating process in a plating section comprising of a series of consecutive plating cells, wherein in a first stage of the plating process a current is applied to the strip entering the first plating cell which current is insufficient to deposit a plating layer from the trivalent Cr-electrolyte, but which is sufficient to provide cathodic protection of the strip in the electrolyte, and wherein in a second stage of the plating process a higher current is applied to the strip to deposit a plating layer comprising chromium metal, chromium carbide and chromium oxide from the trivalent Cr-electrolyte according
- US3316160 discloses a process for preventing a bluish tint on a chromium plated steel strip from a chromic acid plating solution in a plating operation involving two or more vertical plating tanks.
- the current density is high in the first downward and upward pass to effect electrolytic chromium plating.
- the steel strip is then led into a second plating tank and the current density is much lowered in the second downward pass, and any subsequent downward pass, and back to the high level of current density again in the second upward pass.
- This treatment of low and high current density during the downward and upward pass is repeated in every subsequent tank.
- the reduction in current density during the upward pass removes the film of complex chromium oxide that is responsible for the bluish tint.
- a plating section consists of a series of vertical plating cells for obtaining a sufficient total anode length on a limited floor space.
- no current is applied during the first down-pass.
- the first down-pass where the strip enters the plating solution for the first time, the remaining water film sticking to the steel strip surface from the rinsing step is replaced by the electrolyte that is present in the plating cells and also the steel strip is heated to the temperature of the electrolyte.
- the oxide layer that was formed after the pickling step will dissolve rapidly (see figure 1 ).
- a current is applied to the strip entering the electrolyte for the first time (see figure 2 ). It is essential that the current is chosen such that no deposition of a plating layer is achieved, but that the potential of the steel in the electrolyte is shifted such that the steel strip is cathodically protected and does not dissolve.
- the electrolyte in the first plating cell is therefore not being enriched in Fe 2+ , whereas the electrolyte in the first plating cell in the prior art method is being enriched in Fe 2+ .
- This lack of enrichment of the electrolyte in the first plating cell therefore prevents the drag-out of Fe 2+ to subsequent plating cells.
- the current is increased to deposit a plating layer comprising chromium metal, chromium carbide and chromium oxide from the trivalent Cr-electrolyte.
- Iron in the Cr(III) electrolyte deposits on the strip together with chromium. It was found that iron in the Cr-CrCx-CrOx coating adversely affects the corrosion performance. Therefore, it is important to keep the iron level in the Cr(III) electrolyte as low as possible. This is achieved by applying a small current at least in the first down-pass, and preferably also in all other passes which are not in use for plating.
- the method according to the invention can be applied in any inactive plating cell in the series of plating cells through which a strip to be plated is led.
- inactive plating cell the plating cell is meant through which the strip is led, but in which no plating action takes place, for instance when one or more plating cells are skipped, but through which the strip has to be led due to the construction of the entire plating facility.
- the electrolyte is acidic.
- a part of the Cr(III) of the deposit is reduced to Cr-metal and formate is broken down leading to the formation of Cr-carbide. If the Cr(III) is not fully reduced to Cr-metal, then Cr-oxide is also present in the deposit.
- the amount and composition of the deposit depend on the applied current density, mass flux and electrolysis time.
- the threshold value of the current density for entering regime II increases with increasing line speed, because it is related to the mass flux of H + as is explained in the article mentioned above.
- the surface pH increase which is required to deposit Cr(HCOO)(OH) 2 (H 2 O) 3 , is thwarted by the faster replenishment of H + from the bulk of the electrolyte to the electrode surface.
- regime I ends and regime II starts, but it is easy to determine this threshold value by simply monitoring the onset of the deposition of the plating layer as a function of the current density by means of simple experimentation.
- the regimes I - III are visible when the deposition of chromium is plotted against the current density (cf. for example Figure 4 ).
- Regime I is the region where there is a current, but no deposition yet. The surface pH is insufficient for chromium deposition.
- Regime II is when the deposition starts and the total chromium coating weight increases with the current density until it peaks and drops of in regime III where the deposit starts to dissolve: Cr(HCOO)(OH) 2 (H 2 O) 3 + OH - ⁇ [Cr(HCOO)(OH) 3 (H 2 O) 2 ] - + H 2 O
- a high speed continuous plating line is defined as a plating line through which the substrate to be plated, usually in the form of a strip, is moved at a speed of at least 100 m/min.
- a coil of steel strip is positioned at the entry end of the plating line with its eye extending in a horizontal plane. The leading end of the coiled strip is then uncoiled and welded to the tail end of a strip already being processed. Upon exiting the line the coils are separated again and coiled, or cut to a different length and (usually) coiled.
- the electrodeposition process can thus continue without interruption, and the use of strip accumulators prevents the need for speeding down during welding. It is preferable to use deposition processes which allow even higher speeds.
- the method according to the invention preferably allows producing a coated steel substrate in a continuous high speed plating line, operating at a line speed of at least 200 m/min, more preferably of at least 300 m/min and even more preferably of at least 500 m/min.
- a line speed of at least 200 m/min, more preferably of at least 300 m/min and even more preferably of at least 500 m/min.
- the invention is also embodied in an apparatus for performing the method according to the invention.
- this apparatus comprising a series of consecutive plating cells, filled with a suitable trivalent Cr-electrolyte for depositing a plating layer comprising chromium metal, chromium carbide and chromium oxide from the trivalent Cr-electrolyte
- first means are provided for applying a current to the strip entering the electrolyte in the first plating cell which current is insufficient to deposit a plating layer from the trivalent Cr-electrolyte, but which is sufficient to provide cathodic protection of the strip in the electrolyte.
- Second means are provided to apply a higher current to the strip downstream of the first plating cell to deposit a plating layer comprising chromium metal, chromium carbide and chromium oxide from the trivalent Cr-electrolyte.
- the invention is also embodied in an apparatus wherein means are also provided for applying a current to the strip residing in or passing through the electrolyte in a subsequent plating cell in which no plating is to take place, which current is insufficient to deposit a plating layer from the trivalent Cr-electrolyte, but which is sufficient to provide cathodic protection of the strip in the electrolyte residing in said plating cell.
- Subsequent plating cell means any one cell or any combination of cells following the first plating cell.
- a double-walled glass vessel connected with a thermostat bath was filled with a freshly prepared trivalent chromium electrolyte.
- the temperature of the electrolyte was kept constant at 50 ⁇ 1 °C by circulation of hot water through the double-walled glass vessel.
- the composition of the electrolyte was: 120 g l -1 basic chromium sulphate, 100 g l -1 sodium sulphate, and 41.4 g l -1 sodium formate.
- the pH was adjusted to 2.8 measured at 25 °C by adding sulphuric acid.
- the experiments were conducted using a three electrode system (i.e. a working electrode, a counter electrode and a reference electrode) connected to an Autolab PGSTAT303N potentiostat/galvanostat.
- a galvanostat maintains a controlled constant current as defined by the user between the working electrode and the counter electrode, while the potential of the working electrode is monitored as a function of time vs. the potential of the reference electrode.
- the working electrode was a mild steel cylinder insert with an outer diameter of 12 mm and a height of 8 mm, thus having an electro active surface area of ca. 3 cm 2 , fitted in a special holder from Pine Instruments Company.
- the auxiliary (counter) electrode was a meshed strip of a titanium with a catalytic mixed metal oxide coating of iridium oxide and tantalum oxide.
- the reference electrode was a Saturated Calomel Electrode (SCE).
- SCE Saturated Calomel Electrode
- the experiment was repeated, but now a small cathodic current of 2 A dm -2 was applied. By doing so, the potential shifted about 0.6 V in negative direction to -1.2 V vs. SCE.
- the steel cylinder was weighed before and after the electrolysis experiment and the Fe content of the electrolyte was analysed by means of Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES). When no current is applied, an iron concentration of 147 mg l -1 is measured, which corresponds very well with the value calculated from the weight loss of the steel cylinder insert. In contrast, only a negligible amount of iron was measured in the electrolyte, in which the steel electrode was protected against corrosion by applying a small current. No weight loss of the steel cylinder insert was measured and no chromium was deposited on the steel electrode, because the experiment was executed in regime I. Table 1 - Overview of experiments with analysis results. current density A dm -2 electrode potential V vs. SCE Fe weight loss mg l -1 Fe ICP analysis mg l -1 0 (REF) -0.602 V 152 147 -2 ca. -1.2 V 0 1.7
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Description
- This invention relates to a method for electroplating an uncoated steel strip with a plating layer and an improvement thereof.
- In continuous steel strip plating, a cold-rolled steel strip is provided which is usually annealed after cold-rolling to soften the steel by recrystallisation annealing or recovery annealing. After the annealing and before plating the steel strip is first cleaned for removing oil and other surface contaminants. Mostly, an alkaline cleaner is used for this purpose, wherein steel is electrochemically passive, i.e. the steel strip surface is covered with a stable and protective oxide film and therefore the steel will not dissolve in the alkaline cleaner. The alkaline cleaner is a complex mixture of various ingredients. The main component is caustic soda for providing alkalinity, conductivity, and saponification. Other common components are sodium metasilicate, sodium carbonate, phosphates, borates, and surfactants.
- After the cleaning step, the steel strip is pickled in a sulphuric or hydrochloric acid solution for removing the oxide film. Between different treatment steps the steel strip is always rinsed with deionised water to prevent contamination of the solution used for the next treatment step with solution of the preceding treatment step. Consequently the steel strip is thoroughly rinsed after the pickling step. During rinsing and transport of the steel strip to the plating section a fresh thin oxide layer is formed instantly on the bare steel surface.
- The process used in electroplating is called electrodeposition. The part to be plated (the steel strip) is the cathode of the circuit. The anode of the circuit may be made of the metal to be plated on the part (dissolving anode, such as those used in conventional tinplating) or a dimensionally stable anode (which does not dissolve during plating). Both components are immersed in a solution called an electrolyte. At the cathode, the metal ions in the electrolyte solution are reduced at the interface between the solution and the cathode, such that they deposit onto the cathode.
- In many cases electrolytes are acidic solutions. As a consequence the oxide layer that was formed after the pickling step will dissolve rapidly. Bare steel without any oxide film is prone to corrosion. Corrosion means that iron from the steel substrate is oxidised to Fe2+, where the liberated electrons are consumed by the reduction of hydrogen ions or oxygen gas that is dissolved in the electrolyte.
2H+ + 2e- → H2(g)
O2(g) + 4H+ + 4e- → 2H2O
The consequence is that the electrolyte becomes enriched in Fe2+. Depending on the electrolyte these Fe2+-ions are subsequently reduced in the following electroplating step to Fe and this Fe is deposited onto the substrate along with the metal that is intended to be plated onto the substrate. The codeposited iron adversely affects the properties of the plated layer, particularly the corrosion performance. - It is an object of the present invention to provide an improved method for electroplating an uncoated steel strip with a plating layer from a trivalent Cr-electrolyte.
- It is also an object of the present invention to provide a steel strip with a plating layer produced by electroplating an uncoated steel strip using a trivalent Cr-electrolyte with improved properties.
- One or more of the objects is reached by a method for electroplating an uncoated steel strip with a plating layer from a trivalent Cr-electrolyte, wherein the uncoated strip is subjected to a cleaning and pickling step prior to the plating process to remove oxides and any other contaminants present on the surface or surfaces of the strip, and wherein the strip is subsequently subjected to a plating process in a plating section comprising of a series of consecutive plating cells, wherein in a first stage of the plating process a current is applied to the strip entering the first plating cell which current is insufficient to deposit a plating layer from the trivalent Cr-electrolyte, but which is sufficient to provide cathodic protection of the strip in the electrolyte, and wherein in a second stage of the plating process a higher current is applied to the strip to deposit a plating layer comprising chromium metal, chromium carbide and chromium oxide from the trivalent Cr-electrolyte according to the invention.
-
US3316160 discloses a process for preventing a bluish tint on a chromium plated steel strip from a chromic acid plating solution in a plating operation involving two or more vertical plating tanks. In the process the current density is high in the first downward and upward pass to effect electrolytic chromium plating. The steel strip is then led into a second plating tank and the current density is much lowered in the second downward pass, and any subsequent downward pass, and back to the high level of current density again in the second upward pass. This treatment of low and high current density during the downward and upward pass is repeated in every subsequent tank. The reduction in current density during the upward pass removes the film of complex chromium oxide that is responsible for the bluish tint. - The invention is explained by referring to a specific lay-out of a plating section used in industry, but it should be noted that the invention is not intended to be limited thereto, and is applicable to any plating section comprising a series of consecutive plating cells. In an embodiment of the invention a plating section consists of a series of vertical plating cells for obtaining a sufficient total anode length on a limited floor space. In the method known in the art no current is applied during the first down-pass. In the first down-pass, where the strip enters the plating solution for the first time, the remaining water film sticking to the steel strip surface from the rinsing step is replaced by the electrolyte that is present in the plating cells and also the steel strip is heated to the temperature of the electrolyte. When the steel strip is exposed to the electrolyte the oxide layer that was formed after the pickling step will dissolve rapidly (see
figure 1 ). In the method according to the invention a current is applied to the strip entering the electrolyte for the first time (seefigure 2 ). It is essential that the current is chosen such that no deposition of a plating layer is achieved, but that the potential of the steel in the electrolyte is shifted such that the steel strip is cathodically protected and does not dissolve. In the method according to the invention the electrolyte in the first plating cell is therefore not being enriched in Fe2+, whereas the electrolyte in the first plating cell in the prior art method is being enriched in Fe2+. This lack of enrichment of the electrolyte in the first plating cell therefore prevents the drag-out of Fe2+ to subsequent plating cells. In subsequent plating cells the current is increased to deposit a plating layer comprising chromium metal, chromium carbide and chromium oxide from the trivalent Cr-electrolyte. Iron in the Cr(III) electrolyte deposits on the strip together with chromium. It was found that iron in the Cr-CrCx-CrOx coating adversely affects the corrosion performance. Therefore, it is important to keep the iron level in the Cr(III) electrolyte as low as possible. This is achieved by applying a small current at least in the first down-pass, and preferably also in all other passes which are not in use for plating. The method according to the invention can be applied in any inactive plating cell in the series of plating cells through which a strip to be plated is led. With inactive plating cell the plating cell is meant through which the strip is led, but in which no plating action takes place, for instance when one or more plating cells are skipped, but through which the strip has to be led due to the construction of the entire plating facility. In an embodiment of the invention the electrolyte is acidic. - In a study about the deposition mechanism of chromium layers from trivalent chromium electrolytes (J.H.O.J. Wijenberg, M. Steegh, M.P. Aarnts, K.R. Lammers, J.M.C. Mol, Electrodeposition of mixed chromium metal-carbide-oxide coatings from a trivalent chromium-formate electrolyte without a buffering agent, Electrochim. Acta 173 (2015) 819-826.), it was found that the trivalent chromium plating process is very different from regular plating processes, in which the metal ions are directly reduced by an electrical current to metal: Men+ + ne- → Me. This process is known, for instance, from the tinplating process. In contrast, the Cr(III) plating process is based on a fast, stepwise deprotonation of the water ligands in the Cr(III)-complex ion induced by a surface pH increase due to the hydrogen evolution reaction. This leads to the existence of a so called 'regime I', wherein no metal is deposited even though an electrical current is applied (see
figure 3 ). Applying a small current evokes the hydrogen evolution reaction. The removal of H+-ions ions is accompanied by a surface pH increase, which leads to following acid-base reaction:
[Cr(HCOO)(H2O)5]2+ + OH- → [Cr(HCOO)(OH)(H2O)4]+ + H2O
The existence of regime I is unique for the Cr(III) plating process and is absent in regular plating processes. The inventors arrived at the novel idea to make advantageously use of this special feature of the Cr(III) plating process. By applying a small current in the first down-pass not only a small amount of hydrogen gas is formed, but also the potential of the steel shifts in negative direction, a phenomenon known as cathodic protection. Due to the negative potential the steel strip will not corrode anymore. The steel strip is not only protected against corrosion, but also (part of) the iron oxide film will be reduced to iron metal, thereby reducing the iron pick up in the electrolyte even further. Obviously, the water film will still be replaced by the electrolyte when a current is applied and also the steel strip will be heated. The current that must be applied for protecting the steel strip can be very small. The upper limit is restricted by the onset of regime II (seefigure 3 ).
[Cr(HCOO)(OH)(H2O)4]+ + OH- → Cr(HCOO)(OH)2(H2O)3 + H2O
Cr(HCOO)(OH)2(H2O)3 forms a deposit on the cathode. A part of the Cr(III) of the deposit is reduced to Cr-metal and formate is broken down leading to the formation of Cr-carbide. If the Cr(III) is not fully reduced to Cr-metal, then Cr-oxide is also present in the deposit. The amount and composition of the deposit depend on the applied current density, mass flux and electrolysis time. The threshold value of the current density for entering regime II increases with increasing line speed, because it is related to the mass flux of H+ as is explained in the article mentioned above. The surface pH increase, which is required to deposit Cr(HCOO)(OH)2(H2O)3, is thwarted by the faster replenishment of H+ from the bulk of the electrolyte to the electrode surface. Consequently, a higher current density is required with increasing line speed for obtaining the same pH increase at the electrode surface. There is therefore not a fixed threshold value where regime I ends and regime II starts, but it is easy to determine this threshold value by simply monitoring the onset of the deposition of the plating layer as a function of the current density by means of simple experimentation. The regimes I - III are visible when the deposition of chromium is plotted against the current density (cf. for exampleFigure 4 ). Regime I is the region where there is a current, but no deposition yet. The surface pH is insufficient for chromium deposition. Regime II is when the deposition starts and the total chromium coating weight increases with the current density until it peaks and drops of in regime III where the deposit starts to dissolve:
Cr(HCOO)(OH)2(H2O)3 + OH- → [Cr(HCOO)(OH)3(H2O)2]- + H2O
- A high speed continuous plating line is defined as a plating line through which the substrate to be plated, usually in the form of a strip, is moved at a speed of at least 100 m/min. A coil of steel strip is positioned at the entry end of the plating line with its eye extending in a horizontal plane. The leading end of the coiled strip is then uncoiled and welded to the tail end of a strip already being processed. Upon exiting the line the coils are separated again and coiled, or cut to a different length and (usually) coiled. The electrodeposition process can thus continue without interruption, and the use of strip accumulators prevents the need for speeding down during welding. It is preferable to use deposition processes which allow even higher speeds. So the method according to the invention preferably allows producing a coated steel substrate in a continuous high speed plating line, operating at a line speed of at least 200 m/min, more preferably of at least 300 m/min and even more preferably of at least 500 m/min. Although there is no limitation to the maximum speed, it is clear that control of the deposition process, the prevention of drag-out and of the plating parameters and the limitations thereof becomes more difficult the higher the speed. So as a suitable maximum the maximum speed is limited at 900 m/min.
- Although the method according to the invention is applicable to any steel strip, it is preferred to select a strip from:
- ∘ cold-rolled full-hard blackplate, single or double reduced;
- ∘ cold-rolled and recrystallisation annealed blackplate;
- ∘ cold-rolled and recovery annealed blackplate,
- ∘ tinplate, as deposited or flow-melted; snijkanten, tin lost niet op ∘ tinplate, diffusion annealed with an iron-tin alloy consisting of at least 80% of FeSn (50 at.% iron and 50 at.% tin);
- It will be clear that the current density required in regime I to achieve the cathodic protection, but avoid crossing the threshold into regime II is not only dependent on the process conditions like line speed, but also on the nature of the substrate. Also the composition of the electrolyte is relevant, because the kinematic viscosity of the electrolyte influences the threshold value between regime I and regime II (see
figure 4 for the difference between a sodium based bath and a potassium based bath). - The invention is also embodied in an apparatus for performing the method according to the invention. In this apparatus comprising a series of consecutive plating cells, filled with a suitable trivalent Cr-electrolyte for depositing a plating layer comprising chromium metal, chromium carbide and chromium oxide from the trivalent Cr-electrolyte, first means are provided for applying a current to the strip entering the electrolyte in the first plating cell which current is insufficient to deposit a plating layer from the trivalent Cr-electrolyte, but which is sufficient to provide cathodic protection of the strip in the electrolyte. Second means are provided to apply a higher current to the strip downstream of the first plating cell to deposit a plating layer comprising chromium metal, chromium carbide and chromium oxide from the trivalent Cr-electrolyte.
- The invention is also embodied in an apparatus wherein means are also provided for applying a current to the strip residing in or passing through the electrolyte in a subsequent plating cell in which no plating is to take place, which current is insufficient to deposit a plating layer from the trivalent Cr-electrolyte, but which is sufficient to provide cathodic protection of the strip in the electrolyte residing in said plating cell. Subsequent plating cell means any one cell or any combination of cells following the first plating cell.
- The invention will now be described with reference to the following non-limiting examples.
- A double-walled glass vessel connected with a thermostat bath was filled with a freshly prepared trivalent chromium electrolyte. The temperature of the electrolyte was kept constant at 50 ± 1 °C by circulation of hot water through the double-walled glass vessel. The composition of the electrolyte was: 120 g l-1 basic chromium sulphate, 100 g l-1 sodium sulphate, and 41.4 g l-1 sodium formate. The pH was adjusted to 2.8 measured at 25 °C by adding sulphuric acid. The experiments were conducted using a three electrode system (i.e. a working electrode, a counter electrode and a reference electrode) connected to an Autolab PGSTAT303N potentiostat/galvanostat. A galvanostat maintains a controlled constant current as defined by the user between the working electrode and the counter electrode, while the potential of the working electrode is monitored as a function of time vs. the potential of the reference electrode. The working electrode was a mild steel cylinder insert with an outer diameter of 12 mm and a height of 8 mm, thus having an electro active surface area of ca. 3 cm2, fitted in a special holder from Pine Instruments Company.
- The auxiliary (counter) electrode was a meshed strip of a titanium with a catalytic mixed metal oxide coating of iridium oxide and tantalum oxide. The reference electrode was a Saturated Calomel Electrode (SCE). In the reference experiment the steel cylinder was exposed to the electrolyte for 24 h while no current was applied and only the corrosion potential was recorded every 60 s. The corrosion potential was -0.602 V vs. SCE. The experiment was repeated, but now a small cathodic current of 2 A dm-2 was applied. By doing so, the potential shifted about 0.6 V in negative direction to -1.2 V vs. SCE. The steel cylinder was weighed before and after the electrolysis experiment and the Fe content of the electrolyte was analysed by means of Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES). When no current is applied, an iron concentration of 147 mg l-1 is measured, which corresponds very well with the value calculated from the weight loss of the steel cylinder insert. In contrast, only a negligible amount of iron was measured in the electrolyte, in which the steel electrode was protected against corrosion by applying a small current. No weight loss of the steel cylinder insert was measured and no chromium was deposited on the steel electrode, because the experiment was executed in regime I.
Table 1 - Overview of experiments with analysis results. current density A dm-2 electrode potential V vs. SCE Fe weight loss mg l-1 Fe ICP analysis mg l-1 0 (REF) -0.602 V 152 147 -2 ca. -1.2 V 0 1.7
In case of tinplate dissolution of Fe may occur at the edges of the strip where the strip may have been cut to the correct width. The method according to the invention also ensures that no tin dissolves during the passes through the plating cells when no plating takes place.
Claims (7)
- Method for electroplating an uncoated steel strip with a plating layer in a plating section comprising of a series of consecutive plating cells characterised in that the plating layer is deposited in a plating process from a trivalent Cr-electrolyte, wherein the uncoated strip is subjected to a cleaning and pickling step prior to the plating process to remove oxides and any other contaminants present on the surface or surfaces of the strip, and wherein the strip is subsequently subjected to the plating process in the plating section, wherein in a first stage of the plating process a current is applied to the strip entering the first plating cell which current is insufficient to deposit a plating layer from the trivalent Cr-electrolyte, but which is sufficient to provide cathodic protection of the strip in the electrolyte, and wherein in a second stage of the plating process a higher current is applied to the strip to deposit a plating layer comprising chromium metal, chromium carbide and chromium oxide from the trivalent Cr-electrolyte.
- Method according to claim 1 wherein a current is applied to the strip in one, more or all subsequent plating cell in which no plating takes place, wherein the current is insufficient to deposit a plating layer from the electrolyte in the plating cell, but wherein the current is sufficient to provide cathodic protection of the strip in the electrolyte.
- Method according to claim 1 or 2 wherein the Cr-electrolyte comprises chromium(III)sulphate, and one or more of: sodium sulphate, sodium formate, potassium sulphate, potassium formate and sulphuric acid.
- Method according to claim 1 or 2 wherein the Cr-electrolyte comprises chromium(III)sulphate, sodium sulphate, sodium formate and sulphuric acid.
- Method according to claim 1 or 2 wherein the Cr-electrolyte comprises chromium(III)sulphate, potassium sulphate, potassium formate and sulphuric acid
- Method according to claim 1 or 2 wherein the Cr-electrolyte comprises chromium(III)hydroxysulphate (CrOHSO4), formic acid and optionally sulphuric acid and/or NaOH.
- Method according to any one of claims 1 to 6 wherein the anodes in the plating cells comprise a catalytic coating of iridium oxide or a mixed metal oxide.
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DE102018132074A1 (en) * | 2018-12-13 | 2020-06-18 | thysenkrupp AG | Process for producing a metal strip coated with a coating of chromium and chromium oxide based on an electrolyte solution with a trivalent chromium compound |
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SU1730207A1 (en) * | 1989-12-27 | 1992-04-30 | Московский вечерний металлургический институт | Method of chrome-plating |
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