WO2022203095A1 - 황산계 철 전기도금용액의 제2철 이온 제거 방법 - Google Patents
황산계 철 전기도금용액의 제2철 이온 제거 방법 Download PDFInfo
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- WO2022203095A1 WO2022203095A1 PCT/KR2021/003533 KR2021003533W WO2022203095A1 WO 2022203095 A1 WO2022203095 A1 WO 2022203095A1 KR 2021003533 W KR2021003533 W KR 2021003533W WO 2022203095 A1 WO2022203095 A1 WO 2022203095A1
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- iron
- solution
- electroplating
- ferric ions
- plating
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 327
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 161
- 238000009713 electroplating Methods 0.000 title claims abstract description 156
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 229910001447 ferric ion Inorganic materials 0.000 title claims abstract description 135
- 238000000034 method Methods 0.000 title claims abstract description 115
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 9
- 238000007747 plating Methods 0.000 claims abstract description 120
- 230000008929 regeneration Effects 0.000 claims abstract description 81
- 238000011069 regeneration method Methods 0.000 claims abstract description 81
- 239000003792 electrolyte Substances 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 6
- 238000004090 dissolution Methods 0.000 claims description 19
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 18
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 15
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 14
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 238000005275 alloying Methods 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000008139 complexing agent Substances 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 235000001014 amino acid Nutrition 0.000 claims description 5
- 150000001413 amino acids Chemical class 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 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
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 3
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000000174 gluconic acid Substances 0.000 claims description 3
- 235000012208 gluconic acid Nutrition 0.000 claims description 3
- 235000013922 glutamic acid Nutrition 0.000 claims description 3
- 239000004220 glutamic acid Substances 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000004554 glutamine Nutrition 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 57
- 229910001448 ferrous ion Inorganic materials 0.000 description 46
- 239000003638 chemical reducing agent Substances 0.000 description 39
- 230000002829 reductive effect Effects 0.000 description 22
- -1 iron ion Chemical class 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 19
- 238000006722 reduction reaction Methods 0.000 description 19
- 239000010802 sludge Substances 0.000 description 18
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000011572 manganese Substances 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 229910001021 Ferroalloy Inorganic materials 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- 235000010323 ascorbic acid Nutrition 0.000 description 7
- 239000011668 ascorbic acid Substances 0.000 description 7
- 229960005070 ascorbic acid Drugs 0.000 description 7
- 230000003247 decreasing effect Effects 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000002123 temporal effect Effects 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000009825 accumulation Methods 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- SBJKKFFYIZUCET-JLAZNSOCSA-N Dehydro-L-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(=O)C1=O SBJKKFFYIZUCET-JLAZNSOCSA-N 0.000 description 2
- SBJKKFFYIZUCET-UHFFFAOYSA-N Dehydroascorbic acid Natural products OCC(O)C1OC(=O)C(=O)C1=O SBJKKFFYIZUCET-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 235000020960 dehydroascorbic acid Nutrition 0.000 description 2
- 239000011615 dehydroascorbic acid Substances 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 230000013632 homeostatic process Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000284 resting effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- BDDLHHRCDSJVKV-UHFFFAOYSA-N 7028-40-2 Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O BDDLHHRCDSJVKV-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002351 wastewater Substances 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
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/06—Filtering particles other than ions
-
- 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
- C25D21/16—Regeneration of process solutions
- C25D21/18—Regeneration of process solutions of electrolytes
-
- 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
- C25D3/20—Electroplating: Baths therefor from solutions of iron
-
- 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
Definitions
- the present invention relates to a method for effectively removing ferric ions contained in an iron electroplating solution.
- Iron is a material that is manufactured from steel sheet or steel and is used as a general structural material. However, since it lacks corrosion resistance and appearance properties compared to other metals, it is applied to the surface to utilize magnetic properties or to form special-purpose alloys. plating has been carried out.
- a typical plating solution for iron electroplating on the surface of iron uses ferrous ions to maintain high electroplating efficiency.
- ferrous ions are oxidized to ferric iron in the continuous electroplating process, the plating efficiency is sharply increased. There is a problem in that it deteriorates and sludge is generated.
- ferric ions are inevitable in an iron sulfate-based electroplating solution to which an insoluble anode is applied.
- a method of reducing ferric ions in the plating solution to ferrous ions was used, either by filtering off ferric ions from the plating solution to sludge, or by introducing a reducing agent or using an electrolysis method.
- Korean Patent Application No. 2011-0137463 discloses a method for reducing ferric ions to ferrous iron by including ascorbic acid as a reducing agent in an iron sulfate-based electroplating solution.
- ascorbic acid is oxidized to produce dehydroascorbic acid, which sharply decreases the iron electroplating efficiency, and also dehydroascorbic acid is continuously produced. accumulation problem arises.
- an anode and a cathode are installed in an electrolyte and a constant current is applied to generate ferric ions in the first
- a method for reduction to iron ions is disclosed.
- electricity is applied to an electrolyte containing both ferrous ions and ferric ions, a reaction in which ferrous iron is oxidized to ferric ions and a small amount of water decomposition reaction occurs at the anode, whereas iron is mainly produced at the cathode. Since the reaction of electroplating occurs and the reaction of reducing ferric iron to ferrous iron only partially occurs, as a result, ferric ions are rather accumulated. That is, if this method is an electrolyte, the reduction reaction rate of ferric ions at the cathode can be increased by using an additive that inhibits iron electroplating. It is impossible to get rid of my ferric ions.
- the present invention is a method for removing ferric ions from a ferric sulfate-based electroplating solution, wherein a ferric ion is reduced by circulating a ferric sulfate-based electroplating solution containing ferric ions in a solution tank loaded with metallic iron. It provides a method for removing ferric ions in an iron sulfate-based electroplating solution comprising the steps of:
- Equation (1) S is the total surface area (m2) of metallic iron, C max is the allowable maximum ion concentration of ferric iron in solution (g/L), and I conv is the plating time (t p , sec).
- the regeneration step may be performed while performing the plating process.
- the regeneration step is performed while the plating process is performed, and the regeneration step may be performed discontinuously two or more times.
- the regeneration step is started while performing the plating process, and ends during the rest period of the plating process, and the regeneration step may be performed continuously or discontinuously.
- the regeneration step may be started during the rest period of the plating process and may be ended during the plating process or at the rest period after the plating process.
- the regeneration step is performed during a rest period of the plating process, and the regeneration step may be performed continuously or discontinuously.
- the plating process may be performed discontinuously including a rest period, and the regeneration step may be performed during two or more plating processes.
- the metallic iron may be an iron alloy including at least one alloying element selected from the group consisting of Mn, Al, Mg, Li, Na and K.
- the ferroalloy may be an ferroalloy containing an alloying element in an amount of greater than 0% by weight and 3% by weight or less.
- the metallic iron particles may be at least one of a particle, a spiral chip, a plate shape, and a strip.
- the sulfate-based iron electroplating solution may further include a complexing agent.
- the complexing agent is at least one amino acid selected from glycine, glutamic acid and glutamine, formic acid, acetic acid, lactic acid, gluconic acid, oxalic acid, citric acid, NTA (nitrilotriacetic acid) and EDTA (ethylenediamine-N,N,N',N'- It may be at least one compound selected from the group consisting of tetraacetic acid).
- the iron sulfate-based electroplating solution may have a temperature of 80° C. or less and a pH of 1.0 to 4.0.
- the method includes an electroplating cell in which electroplating is performed by applying an electric current; a circulation tank circulating the electroplating cell and the electroplating solution; and a dissolution tank circulating the circulation tank and the electroplating solution, wherein the metallic iron is charged, and dissolving metallic iron to remove ferric ions from the electroplating solution, wherein the electroplating solution of the circulation tank is supplied to the dissolution tank It can be performed by an iron-based electroplating apparatus having a pump and a filter for preventing the metal iron from flowing into the circulating tank.
- reduction in electroplating efficiency can be prevented by effectively removing ferric ions that are continuously accumulated during continuous electroplating, and sludge due to accumulation of ferric ions can be prevented.
- ferric ions are reduced to ferrous ions and metallic iron is dissolved to supply ferrous ions, the concentration of ferrous ions in the iron electroplating solution can be maintained constant.
- FIG. 1 is a diagram schematically illustrating a temporal relationship between plating and electrolyte regeneration, and is a diagram schematically illustrating continuous regeneration of an electrolyte during a continuous plating process.
- FIG. 2 is a diagram schematically illustrating a temporal relationship between plating and electrolyte regeneration, and schematically illustrates an example of discontinuously performing regeneration of an electrolyte during a continuous plating process.
- FIG. 3 is a diagram schematically illustrating a temporal relationship between plating and electrolyte regeneration, and schematically illustrates an example of starting the regeneration of the electrolyte while performing the plating process and terminating the regeneration process of the electrolyte during the rest period of the plating process.
- FIG. 4 is a diagram schematically illustrating a temporal relationship between plating and electrolyte regeneration, and schematically illustrates an example of starting electrolyte regeneration before applying a current for plating and terminating electrolyte regeneration in a rest period after the plating process is finished.
- FIG. 5 is a diagram schematically illustrating a temporal relationship between plating and electrolyte regeneration, and schematically illustrates an example in which an electrolyte regeneration process is performed during a rest period between plating processes.
- FIG. 6 is a diagram schematically illustrating a temporal relationship between plating and electrolyte regeneration, and is a diagram schematically illustrating an example of continuously performing electrolyte regeneration in at least two plating processes and a rest period between plating processes.
- FIG. 7 is a schematic representation of an apparatus according to the method of the present invention.
- Example 8 is a photograph of the initial solution according to Example 1 and the solution after 1 hour, 2 hours, and 3 hours have elapsed after pure iron is added and dissolved in the initial solution.
- An embodiment of the present invention reduces the concentration of ferric ions accumulated in the electroplating solution when performing iron electroplating using an iron sulfate-based electroplating solution in an electroplating facility to which an insoluble anode is applied, and reduces the concentration of ferric ions during plating.
- An object of the present invention is to provide a method for supplying consumed ferrous ions.
- the present invention provides a method of contacting metallic iron with ferric ions generated during a continuous plating operation in an electroplating facility using an insoluble anode. It is intended to reduce the concentration of ferric iron in the iron electroplating solution by reducing it.
- the water decomposition reaction and the oxidation reaction of ferrous ions to ferric ions occur simultaneously. Since the potential at which the oxidation reaction of ferrous ions occurs is lower than the potential at which the water decomposition reaction occurs, the voltage at which the oxidation reaction of ferrous ions occurs is higher when the low current operation is performed because the voltage is lowered. In addition, when a complexing agent is used to prevent sludge, the oxidation reaction of ferrous ions is further accelerated because the ferric ions maintain a more stable state in the electrolyte.
- the present inventors have attempted to provide a method for preventing a decrease in iron electroplating efficiency by reducing ferric ions generated during continuous plating in a sulfate-based iron electroplating solution again.
- the present invention suppresses the generation of sludge in a solution by reducing and removing ferric ions that are continuously accumulated in an iron electroplating facility to which an insoluble anode is applied, and supplies the iron ions consumed during electroplating, thereby increasing the concentration of iron ions in the solution. wants to keep it constant. Through this, even when continuous plating is performed, high electroplating efficiency can be maintained.
- the present invention can maintain a constant pH of the electroplating solution while reducing the concentration of ferric ions in the electroplating solution, thereby maintaining a constant plating efficiency, and simplifying the management of the iron electroplating solution. It is easy to use and can be used continuously for a long time.
- the present inventors have devised a method of using metallic iron, which is a main component of an iron electroplating solution, as a reducing agent.
- metallic iron in the present invention is used as a reducing agent for removing ferric ions in the iron electroplating solution.
- iron When iron is used as a reducing agent, it reacts with hydrogen ions or ferric ions in the solution and is eluted, thereby reducing the ferric ions in the solution to ferrous ions, and furthermore, it is possible to supply ferrous ions.
- the metallic iron used as the reducing agent may be pure iron or ferroalloy.
- the alloying element of the ferroalloy may be an element that has stronger oxidizing properties than iron and is not easily precipitated in electroplating, for example, at least one selected from the group consisting of Mn, Al, Mg, Li, Na and K. can be In the case of using such an ferroalloy, it is possible to further increase the elution rate by reacting with hydrogen ions or ferric ions in the solution. More preferably, the alloying element may be at least one selected from the group consisting of Mn and Al.
- the metal iron used as the reducing agent preferably has an alloying element content of 3 wt% or less.
- the alloying element with strong oxidizing property reacts with oxygen introduced in the atmosphere and hydrogen ions in the solution, even if there are almost no ferric ions in the solution, and can be continuously eluted. In this case, the pH of the plating solution is excessively increased.
- the ion concentration of the alloying element in the solution increases, and it is mixed into the iron electroplating layer during the electroplating process, so that the desired pure iron electroplating layer cannot be obtained.
- the metallic iron used as the reducing agent in the present invention is pure iron or iron alloy, and the shape is not limited, and may be in the form of particles such as a sphere, a spiral chip, a plate shape, or a strip shape.
- the metal iron has a plate shape or a strip shape, it can be added to an appropriate size by cutting when it is put into the dissolution tank. can be prevented, and furthermore, a by-product generated in a manufacturing process such as a steel sheet can be used as a reducing agent, so that the manufacturing cost can be reduced, which is more preferable.
- the filling rate is high, so that the contact area with the solution can be increased, and thus, it is preferable to prevent the volume of the dissolution tank from becoming excessively large.
- the size of the metal iron used as the reducing agent is not particularly limited as it can be appropriately selected in consideration of plating equipment, reduction efficiency, and the like.
- plate-shaped or strip-shaped metallic iron can be used with a thickness of 0.1 to 5 mm, and it does not impede only the flow of the solution, such as cutting them to an appropriate size, or arranging plates or strips stacked at equal intervals. If arranged in such a way that the reduction effect of ferric iron can be obtained in the same way, the area of the plate shape or the strip is not particularly limited.
- particles having an average diameter of 0.1 mm to 10 mm for example 0.5 mm, 0.7 mm, 1 mm or more and 5 mm, 7 mm or 10 mm or less can be used.
- the pH may be excessively increased by reacting with hydrogen ions in the solution, and the iron particles may flow into the electroplating cell and damage the plating surface.
- the size of metallic iron is too large, the reaction area may be reduced, so that ferric ions may not be effectively removed, and a large amount of metallic iron is required. Therefore, it is preferable to select metallic iron having an appropriate size within the above range according to the iron electroplating equipment capacity and the plating speed.
- Ferrous ions in the electroplating solution are reduced to metallic iron at -0.44V or less compared to the standard hydrogen electrode, and oxidized to ferric ions when it is 0.77V or more.
- water is electrolyzed at 1.23V or higher to generate oxygen gas. Therefore, when iron electroplating is performed in an electroplating facility having an insoluble anode, an oxidation reaction of ferrous iron in which ferrous ions are oxidized to ferric ions and a decomposition reaction in which water is decomposed occurs in the anode.
- ferrous ions are reduced to metallic iron and plated, and ferric ions are partially reduced to ferrous ions.
- the ratio of each reaction generation amount may be slightly different depending on the current density, electrode, and solution characteristics. Since the ratio of the electroplating amount is higher than the reduction reaction amount of ferric iron, and the oxidation reaction of ferrous iron and the decomposition reaction of water occur at the anode, when electroplating is performed by applying an electric current, the concentration of ferric ions in the solution is can only increase continuously.
- the rate at which ferric ions are generated in the iron electroplating solution increases in proportion to the amount of current applied for the iron electroplating or the plating rate. Therefore, it is desirable to control the ferric production rate by the electroplating not to exceed the ferric iron removal rate by the metallic iron so that the ferric ions do not continuously increase.
- the present inventors have confirmed through numerous experiments that the continuous accumulation and increase of ferric ions can be prevented by using metallic iron as a reducing agent in an appropriate amount according to the electroplating rate. That is, if the contact area between the metallic iron and the solution is sufficiently large, the amount of reaction by which ferric ions are reduced to ferrous iron increases, so that the increase in ferric ions can be suppressed.
- the production rate of ferric ions can be expressed as a ⁇ I conv , where a is the production rate constant of ferric ions, I conv is the converted current per unit time, and the converted current I conv is the plating time (t m) . , sec) divided by the total amount of current (I) applied during the regeneration of the electrolyte, that is, the regeneration time (t n , sec) for the reduction of ferric ions, which can be expressed as the following formula, where the unit is is A.
- FIG. 1 illustrates a case in which regeneration for reduction of ferric ions is continuously performed while a plating process is performed by applying an electric current (I) as an embodiment for the case of continuous plating and continuous regeneration, and the plating process A regeneration process may be performed during the process.
- I electric current
- the current application time (t p ) and the regeneration time (t r ) are the same, and in this case, the converted current I conv is equal to the average current applied to the plating cell per unit time.
- 2 is an exemplary embodiment for continuous plating and discontinuous regeneration, in which the concentration of divalent iron ions in the electrolyte exceeds a permissible value in the process of continuously performing a plating process by applying an electric current (I) intermittently; Indicates that the regeneration process is performed.
- I electric current
- 3 is an embodiment of the discontinuous plating and continuous regeneration, wherein the regeneration process is started when the concentration of divalent iron ions in the electrolyte exceeds a permissible value during the plating process by applying an electric current (I). It indicates that the regeneration process is terminated after the regeneration process is continued for a certain period of time during the rest period of the plating process. In this case, the current application time (t p ) and the regeneration time (t r ) may be the same or different. 3 shows that the regeneration process is continuously performed once, those skilled in the art will readily understand that it can be performed intermittently by combining the embodiment of FIG. 2 .
- 4 is another embodiment for the case of discontinuous plating and continuous regeneration, before the plating process is performed by applying the current (I), that is, the regeneration process is started during the rest period of the plating process in which the current (I) is not applied. This indicates that the regeneration process is maintained during the plating process, and the regeneration process is continued for a certain period of time until the rest period after the end of the plating process, and then ends.
- This embodiment can be suitably performed in the case of using the electrolyte used in the previous plating process.
- the current application time (t p ) and the regeneration time (t r ) may be different. 4 shows that the regeneration process is continuously performed once, those skilled in the art will readily understand that it can be performed intermittently by combining the embodiment of FIG. 2 .
- the current application time (t p ) and the regeneration time (t r ) may be the same.
- 5 is another embodiment for the case of discontinuous plating and continuous regeneration, showing that the regeneration process is performed during the rest period of the plating process in which current I is not applied.
- the current application time (t p ) and the regeneration time (t r ) may be the same or different.
- 5 shows that one regeneration process is continuously performed, but may also be performed intermittently by combining the embodiment of FIG. can In this case, the current application time (t p ) and the regeneration time (t r ) may be the same or different.
- 6 is another embodiment for the case of discontinuous plating and continuous regeneration, wherein the plating process is performed discontinuously with plating-interruption-plating, and the regeneration process is continuously performed during plating and resting period.
- the current application time (t p ) and the regeneration time (t r ) may be different. 6 shows that the regeneration process is continuously performed once, it may be performed intermittently by combining the embodiment of FIG. 2, and the regeneration process may be started or ended during the plating process. In this case, the current application time (t p ) and the regeneration time (t r ) may be the same.
- the concentration of ferric ions in the iron electroplating solution is C (g/L) and the total surface area of metallic iron injected as a reducing agent is S (m2)
- the ferric ions are reduced by the reducing agent
- C represents the equilibrium concentration
- a/b is a value that can be obtained experimentally, and as a result of the measurement by the present inventors, a has an almost constant value regardless of the solution and electrode, and b is Mn in metallic iron added as a reducing agent, It has a tendency to increase as the content of alloying elements such as Al increases, and in the case of pure iron, a/b was confirmed to be 0.01.
- ferric ions when a large amount of ferric ions is included in the sulfate-based electroplating solution, the ferric ions form hydroxide and sludge is generated. Since the reduction reaction does not occur, the reducing power of metallic iron does not appear in a normal plating solution. Therefore, in order to reduce the ferric ions by a corrosion reaction with metallic iron, it is preferable to use a complexing agent to prevent the ferric ions from being precipitated in the form of sludge.
- the complexing agent that can be used in the present invention as long as it is commonly used in electroplating, it can be suitably used in the present invention, and is not particularly limited, but, for example, a compound having a carboxyl group may be used, and specifically, glycine and amino acids such as glutamic acid and glutamine; acids containing one carboxyl group, such as formic acid, acetic acid, lactic acid, and gluconic acid; and acids having two or more carboxyl groups, such as oxalic acid, citric acid, nitrilotriacetic acid (NTA), and ethylenediamine-N,N,N',N'-tetraacetic acid (EDTA).
- NTA nitrilotriacetic acid
- EDTA ethylenediamine-N,N,N',N'-tetraacetic acid
- an electroplating cell 1 in which iron electroplating is performed by applying an electric current, an electroplating solution is supplied to the electroplating cell 1, and an electroplating cell 1 It includes a circulation tank (2) supplied with the electroplating solution from. That is, the electroplating solution circulates between the electroplating cell 1 and the circulation tank 2 .
- ferrous ions are supplied to the circulation tank 2 , and the electroplating solution containing the ferrous ions is supplied to the electroplating cell 1 , and the electroplating solution in the electroplating cell 1 .
- the concentration of ferrous ions contained in the ferrous ions may be maintained constant.
- the electroplating solution in which the concentration of ferric ions is increased by the electroplating in the electroplating cell 1 is transferred to the circulation tank 2 .
- the electroplating solution containing ferric ions supplied from the electroplating cell (1) to the circulation tank (2) is circulated to the dissolution tank (3).
- the dissolution tank 3 is charged with metallic iron.
- the electroplating solution supplied to the dissolution tank 3 dissolves metallic iron in the dissolution tank 3, and in this process, the ferric ions in the electroplating solution are reduced to ferrous ions by the metallic iron, and the electroplating solution The content of ferric ions in the water is reduced.
- the circulation of the electroplating solution from the circulation tank 2 to the dissolution tank 3 may be performed by driving the pump 4 as shown in FIG. 1 .
- the electroplating solution in the dissolution tank 3 having a reduced content of ferric ions is supplied to the circulation tank 2 and then to the electroplating cell 1 .
- the filtering means (5) is to prevent the metal iron particles or impurity particles charged in the dissolution tank (3) from flowing into the circulation tank (2) together with the electroplating solution.
- the metallic iron particles are caught between the roll and the strip, and the strip may be stamped, causing dent defects. .
- the filtration means 5 is not particularly limited as can be suitably applied in the present invention as long as it is a means for separating solids in solution in general, and for example, a filter or a filtration network may be mentioned.
- ferric ions present in the iron electroplating solution react with metallic iron.
- ferric ions are reduced to ferrous ions, and metallic iron is eluted as ferrous ions, thereby removing ferric ions from the solution.
- the iron sulfate-based electroplating solution to which the present invention is applied is not particularly limited as long as it is at a temperature of 80° C. or less, unless it causes freezing of the plating solution and a change in viscosity, and more preferably 0° C. or higher; It can be carried out at 80° C. or less.
- the pH of the electroplating solution is not particularly limited as it does not significantly affect the reduction of ferric iron, but in terms of electroplating efficiency, it is preferably pH 1.0 to 4.0, and more preferably 2.0 to 3.0 days.
- ferrous sulfate as a raw material for ferrous iron and using ferric sulfate as a raw material for ferric iron, ferrous ion concentration, ferric ion concentration, and ferrous ion concentration and ferric ion concentration
- the total concentration (T-Fe) was prepared as a sulfate-based iron electroplating solution as shown in Table 1 below.
- the pH of the iron electroplating solution was adjusted as shown in Table 1 using sulfuric acid and sodium hydroxide, and glutamine as a complexing agent was added so as to prevent ferric ions from precipitating into the sludge so as to have a molar concentration of 0.5 times the iron ions.
- plating efficiency was measured by electroplating at a current density of 40 ASD immediately after preparing the solution and in a solution from which ferric iron was removed using a metal iron plate as a reducing agent.
- the iron electroplating solutions prepared to contain a large amount of ferric ions in Reference Examples 1 and 2 had plating efficiencies of 54% and 63%, respectively, and the lower the pH, the lower the plating efficiency. .
- the T-Fe concentration obtained by adding the ferric ion concentration, the ferrous ion concentration, and the ferric ion concentration to the obtained iron electroplating solution was respectively measured, and the results are shown in Table 2.
- the pH of the iron electroplating solution was adjusted as shown in Table 2 using sulfuric acid and sodium hydroxide, and amino acids or citric acid were added so as to prevent ferric ions from precipitating into the sludge so as to have a molar concentration of 0.5 times the iron ions.
- the plating efficiency was measured by electroplating at a current density of 40 ASD in the solution obtained by this method and removing ferric iron using a reducing agent and immediately after preparing the solution.
- Comparative Examples 1 and 2 the reduction treatment was performed in the same manner as in Example 1, except that 16 g/L of ascorbic acid was added as a reducing agent to the initial solutions of Reference Examples 1 and 2 to reduce ferric ions to ferrous ions. A reduced iron electroplating solution was obtained.
- An example using the initial solution of Reference Example 1 is Comparative Example 1
- an example using the initial solution of Reference Example 2 is Comparative Example 2.
- the ferric ion concentration, the ferrous ion concentration, and the ferric ion concentration of the prepared iron electroplating solution were measured for T-Fe, respectively, and the results are shown in Table 3.
- Comparative Examples 3 and 4 reduction treatment was performed in the same manner as in Example 1, except that 12 g/L of sodium sulfite was added to the initial solution of Reference Examples 1 and 2 as a reducing agent and maintained at 50° C. for 3 hours. An iron electroplating solution was prepared.
- An example using the initial solution of Reference Example 1 is Comparative Example 3
- an example using the initial solution of Reference Example 2 is Comparative Example 4.
- the ferric ion concentration, the ferrous ion concentration, and the T-Fe concentration obtained by adding the ferric ion concentration of the prepared iron electroplating solution were respectively measured, and the results are shown in Table 4.
- ferrous sulfate was dissolved so that the iron ion (T-Fe) concentration was about 50 g/L, and glutamine, a type of amino acid, as a complexing agent was added so as to have a molar concentration of 0.5 times the iron ion concentration.
- glutamine a type of amino acid, as a complexing agent was added so as to have a molar concentration of 0.5 times the iron ion concentration.
- a metal iron plate of pure iron with a thickness of 0.5 mm or ferroalloy with different Mn content was cut to a size of 1 dm 2 and charged into the melting tank at regular intervals so as not to overlap each other.
- the surface area of the metallic iron in contact with the solution was adjusted by varying the number of metallic iron plates charged into the dissolution tank, and the input area (dm 2 ) of the reducing agent accordingly is as shown in Table 5.
- a copper plate having a plating area of 1 dm 2 was degreased in advance and plated continuously at a current of 40 A at regular time intervals for 2 minutes per time, and plated a total of 5 times per hour to obtain an average current of 6.7 A.
- Examples 3 to 4 and Comparative Examples 6 and 7 are examples in which iron plates cut into 1 dm 2 size of pure iron as a reducing agent were charged at regular intervals by varying the number of inputs. effect can be checked.
- Comparative Examples 6 to 7 were charged so that the surface area of the metallic iron plate was 2dm 2 and 4dm 2 . Unlike Comparative Example 5 in which metallic iron was not charged, the concentration of ferric ions did not significantly increase, and the plating Efficiency did not decrease significantly, but showed a tendency to increase more slowly than the concentration of ferric ions compared to the initial solution.
- Examples 5 to 7 and Comparative Example 8 are examples in which an iron alloy sheet containing about 3% of Mn as a reducing agent was sheared to a size of 1 dm 2 and charged at regular intervals by varying the number of inputs, and the surface area of the Mn iron alloy It can be confirmed the effect of inhibiting the production of ferric ions according to the
- the Mn-containing iron alloy plate had a surface area of 4dm 2 or more, but the concentration of ferric ions was decreased compared to the initial solution.
- Comparative Example 8 in which the area of the iron alloy plate was charged to be 2dm 2 , the pH decreased and the concentration of ferric ions gradually increased as plating proceeded.
- Comparative Examples 9 to 12 as an example of using an iron alloy sheet containing about 5% by weight of Mn as a reducing agent, the effect of inhibiting the generation of ferric ions according to the Mn content can be confirmed.
- the concentration of ferric ions was greatly reduced even when a small amount of the iron alloy Mn was used, and the plating efficiency was maintained constant.
- the content of Mn in the solution increased, the pH rapidly increased, and fine sludge was generated in the electroplating solution during plating.
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Abstract
Description
구분 | 초기 용액 | ||||
T-Fe(g/L) | 제2철(g/L) | 착화제 | pH | 도금효율(%) | |
참고예 1 | 50.1 | 9.3 | 글루타민 | 2.3 | 54 |
참고예 2 | 49.8 | 9.9 | 2.9 | 63 |
구분 | 환원제 | 환원처리 용액 | ||||
T-Fe(g/L) | 제2철(g/L) | pH | 슬러지 | 도금효율(%) | ||
실시예 1 | 금속 철 | 55.8 | 0.4 | 3.1 | 미발생 | 82 |
실시예 2 | 금속 철 | 54.2 | 1.0 | 3.7 | 미발생 | 85 |
구분 | 처리방법 | 환원처리 용액 | ||||
환원제 | T-Fe(g/L) | 제2철(g/L) | pH | 슬러지 | 도금효율(%) | |
비교예 1 | 아스코르브산 16g/L | 50.0 | 2.2 | 2.0 | 미발생 | 46 |
비교예 2 | 아스코르브산 16g/L | 50.2 | 2.1 | 2.6 | 미발생 | 49 |
구분 | 처리방법 | 환원처리 용액 | ||||
환원제 | T-Fe(g/L) | 제2철(g/L) | pH | 슬러지 | 도금효율(%) | |
비교예 3 | 아황산나트륨 12g/L | 50.1 | 10.2 | 2.2 | 미발생 | 49 |
비교예 4 | 아황산나트륨 12g/L | 50.1 | 10.9 | 2.8 | 미발생 | 57 |
Claims (14)
- 황산계 철 전기도금 용액 내 제2철 이온을 제거하는 방법으로서,제2철 이온을 포함하는 황산계 철 전기도금 용액을 금속 철이 장입된 용액조에 순환시켜 제2철 이온을 환원시키는 재생단계를 포함하며,상기 금속 철은 다음 식 (1)을 만족하는 함량으로 장입되는 것인 황산계 철 전기도금 용액 내 제2철 이온을 제거하는 방법.S ≥0.01 I conv/C max (1)식 (1)에서, S는 금속 철의 전체 표면적(㎡)이고, C max는 용액 내 제2철의 최대 이온농도 허용치(g/L)이며, I avg는 도금시간(t p, sec) 동안 전기도금셀에 인가된 전류(I)의 총량을 전해액 중 제2철 이온의 환원을 위한 재생시간(t r, sec)으로 나눈 환산전류(A)로, 다음 식 (2)로 나타낸다.
- 제1항에 있어서, 도금공정을 수행하는 중에 상기 재생단계를 수행하는 것인, 황산계 철 전기도금 용액 내 제2철 이온을 제거하는 방법.
- 제1항에 있어서, 도금공정을 수행하는 중에 재생단계를 수행하며, 상기 재생단계는 2회 이상 불연속적으로 수행하는 것인, 황산계 철 전기도금 용액 내 제2철 이온을 제거하는 방법.
- 제1항에 있어서, 도금공정을 수행하는 중에 재생단계를 개시하고, 도금공정의 휴지기에 재생단계를 종료하며, 상기 재생단계는 연속적 또는 불연속적으로 수행하는 것인, 황산계 철 전기도금 용액 내 제2철 이온을 제거하는 방법.
- 제1항에 있어서, 도금공정의 휴지기에 재생단계를 개시하고, 도금공정 중 또는 도금공정 후의 휴기지에 재생단계를 종료하는 것인, 황산계 철 전기도금 용액 내 제2철 이온을 제거하는 방법.
- 제1항에 있어서, 도금공정의 휴지기 중에 재생단계를 수행하며, 상기 재생단계는 연속적 또는 불연속적으로 수행하는 것인, 황산계 철 전기도금 용액 내 제2철 이온을 제거하는 방법.
- 제1항에 있어서, 도금공정은 휴지기를 포함하여 불연속적으로 수행되고, 2회 이상의 도금공정 동안 재생단계를 수행하는 것인, 황산계 철 전기도금 용액 내 제2철 이온을 제거하는 방법.
- 제1항에 있어서, 상기 금속 철은 Mn, Al, Mg, Li, Na 및 K로 이루어진 군으로부터 선택되는 적어도 하나의 합금원소를 포함하는 합금 철인, 황산계 철 전기도금 용액 내 제2철 이온을 제거하는 방법.
- 제8항에 있어서, 상기 합금 철은 합금원소를 0중량% 초과, 3 중량% 이하의 함량으로 포함하는 합금 철인, 황산계 철 전기도금 용액 내 제2철 이온을 제거하는 방법.
- 제1항에 있어서, 상기 금속 철 입자는 입자, 나선형의 칩, 판상 및 스트립 중 적어도 하나인, 황산계 철 전기도금 용액 내 제2철 이온을 제거하는 방법.
- 제1항에 있어서, 상기 황산계 철 전기도금 용액은 착화제로 더 포함하는 것인, 황산계 철 전기도금 용액 내 제2철 이온을 제거하는 방법.
- 제11항에 있어서, 상기 착화제는 글리신, 글루탐산 및 글루타민으로부터 선택되는 적어도 하나의 아미노산, 개미산, 아세트산, 유산, 글루콘산, 옥살산, 구연산, NTA(nitrilotriacetic acid) 및 EDTA(ethylenediamine-N,N,N',N'-tetraacetic acid)로 이루어진 그룹으로부터 선택되는 적어도 하나의 화합물인, 황산계 철 전기도금 용액 내 제2철 이온을 제거하는 방법.
- 제1항에 있어서, 상기 황산계 철 전기도금 용액은 온도 80℃ 이하 및 pH 1.0 내지 4.0인, 황산계 철 전기도금 용액 내 제2철 이온을 제거하는 방법.
- 제1항 내지 제13항 중 어느 한 항에 있어서, 상기 방법은전류를 인가하여 전기도금이 수행되는 전기도금셀;상기 전기도금셀과 전기도금액을 순환하는 순환조;상기 순환조와 전기도금액을 순환하며, 상기 금속 철이 장입되고, 금속 철을 용해하여 상기 전기도금액으로부터 제2철 이온을 제거하는 용해조;를 포함하고, 상기 순환조의 전기도금액을 용해조로 공급하는 펌프 및 용해조의 금속 철이 순환조로 유입을 방지하는 필터를 구비하는 철계 전기도금 장치에 의해 수행되는 것인 방법.
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EP21933323.4A EP4317537A4 (en) | 2021-03-22 | 2021-03-22 | METHOD FOR REMOVING FERRIC ION FROM A SULFATE-BASED IRON ELECTROPLATING SOLUTION |
JP2023555600A JP2024509312A (ja) | 2021-03-22 | 2021-03-22 | 硫酸系鉄電気めっき溶液の第2鉄イオン除去方法 |
US18/280,811 US20240150924A1 (en) | 2021-03-22 | 2021-03-22 | Method for removing ferric ions from sulfate-based iron electroplating solution |
KR1020237036190A KR20230159574A (ko) | 2021-03-22 | 2021-03-22 | 황산계 철 전기도금용액의 제2철 이온 제거 방법 |
CN202180096238.7A CN117460867A (zh) | 2021-03-22 | 2021-03-22 | 去除硫酸基铁电镀溶液中的三价铁离子的方法 |
PCT/KR2021/003533 WO2022203095A1 (ko) | 2021-03-22 | 2021-03-22 | 황산계 철 전기도금용액의 제2철 이온 제거 방법 |
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KR (1) | KR20230159574A (ko) |
CN (1) | CN117460867A (ko) |
WO (1) | WO2022203095A1 (ko) |
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JPS63259089A (ja) | 1987-04-16 | 1988-10-26 | Kawasaki Steel Corp | 鉄系めつき液中の第二鉄イオン電解還元方法 |
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JPH06306697A (ja) * | 1993-04-23 | 1994-11-01 | Kawasaki Steel Corp | 鉄系電気めっき液中の3価のFeイオンの高効率還元方法 |
JPH09165698A (ja) * | 1995-12-15 | 1997-06-24 | Toyota Motor Corp | 鉄系めっき液中の第二鉄イオンの電解還元方法 |
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2021
- 2021-03-22 US US18/280,811 patent/US20240150924A1/en active Pending
- 2021-03-22 CN CN202180096238.7A patent/CN117460867A/zh active Pending
- 2021-03-22 KR KR1020237036190A patent/KR20230159574A/ko unknown
- 2021-03-22 WO PCT/KR2021/003533 patent/WO2022203095A1/ko active Application Filing
- 2021-03-22 JP JP2023555600A patent/JP2024509312A/ja active Pending
- 2021-03-22 EP EP21933323.4A patent/EP4317537A4/en active Pending
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JPS63259089A (ja) | 1987-04-16 | 1988-10-26 | Kawasaki Steel Corp | 鉄系めつき液中の第二鉄イオン電解還元方法 |
JPH06181533A (ja) | 1992-03-12 | 1994-06-28 | Hitachi Ltd | コンパクトビデオカメラ,光学システム,電子ズーム付きビデオカメラ用レンズ及びコンパクトビデオカメラシステム |
JPH06306697A (ja) * | 1993-04-23 | 1994-11-01 | Kawasaki Steel Corp | 鉄系電気めっき液中の3価のFeイオンの高効率還元方法 |
KR0138617B1 (ko) * | 1994-12-19 | 1998-07-15 | 김만제 | 철-망간 도금액 중의 제2철 이온제거방법 |
JPH09165698A (ja) * | 1995-12-15 | 1997-06-24 | Toyota Motor Corp | 鉄系めっき液中の第二鉄イオンの電解還元方法 |
JPH10102300A (ja) * | 1996-09-27 | 1998-04-21 | Nippon Parkerizing Co Ltd | 不溶性陽極を用いる鉄含有金属めっき用めっき液の管理方法 |
KR20110137463A (ko) | 2010-06-17 | 2011-12-23 | 주식회사 실리콘웍스 | 출력 드라이버의 출력 전압 안정화 회로 |
CN210163184U (zh) * | 2019-06-05 | 2020-03-20 | 山东申龙水务有限公司 | 一种新型高级氧化铁盐污泥三价铁还原成二价铁装置 |
Non-Patent Citations (1)
Title |
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See also references of EP4317537A4 |
Also Published As
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KR20230159574A (ko) | 2023-11-21 |
JP2024509312A (ja) | 2024-02-29 |
EP4317537A4 (en) | 2024-05-22 |
CN117460867A (zh) | 2024-01-26 |
US20240150924A1 (en) | 2024-05-09 |
EP4317537A1 (en) | 2024-02-07 |
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