WO2014178396A1 - Niめっき鋼板及びNiめっき鋼板の製造方法 - Google Patents
Niめっき鋼板及びNiめっき鋼板の製造方法 Download PDFInfo
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- WO2014178396A1 WO2014178396A1 PCT/JP2014/061967 JP2014061967W WO2014178396A1 WO 2014178396 A1 WO2014178396 A1 WO 2014178396A1 JP 2014061967 W JP2014061967 W JP 2014061967W WO 2014178396 A1 WO2014178396 A1 WO 2014178396A1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
- B32B15/015—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium the said other metal being copper or nickel or an alloy thereof
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
- C25D5/611—Smooth layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
Definitions
- the present invention relates to a Ni-plated steel sheet and a method for producing a Ni-plated steel sheet.
- a chemical conversion film containing various elements such as zirconium (Zr), phosphorus (P), chromium (Cr), titanium (Ti), manganese (Mn), and aluminum (Al) is formed on the nickel (Ni) plating.
- the steel plate for containers is used as one of metal materials for manufacturing metal containers for the purpose of preserving beverages and foods (see, for example, Patent Documents 1 to 3).
- a Ni-plated steel sheet having such a chemical conversion treatment film has excellent weldability by Ni plating and excellent adhesion to a film or paint by the chemical conversion treatment film.
- Patent Document 4 discloses a technique for improving the adhesion of Ni plating by performing Ni strike plating and forming Ni plating through a cleaning process.
- This Ni-plated steel sheet is used as one of the frame materials of a color cathode ray tube, and can exhibit excellent weldability by Ni plating and excellent plating adhesion by Ni strike plating.
- Japanese Laid-Open Patent Publication No. 11-106952 Japanese Laid-Open Patent Publication No. 11-106954 Japanese Unexamined Patent Publication No. 2007-284789 Japanese Unexamined Patent Publication No. 6-330375
- Ni-plated steel sheets described in Patent Documents 1 to 3 have poor corrosion resistance against highly corrosive contents such as acidic beverages. Therefore, these Ni-plated steel sheets are mainly used in cans for weakly corrosive contents such as three-piece welded cans for beverage cans, and cans for highly corrosive contents. There was a problem that it cannot be used as a material.
- the Ni-plated steel sheet described in Patent Document 4 uses a so-called Watt bath for forming the Ni plating layer. In Ni plating using the Watt bath, even if the Ni plating amount is increased, the surface unevenness becomes coarse. As a result, a dense film is not formed, and corrosion resistance is not improved due to the presence of film defects. Moreover, although the Ni plating formed by the watt bath containing no chloride ions is dense, the surface has few irregularities, so that the weldability is lowered.
- One method for improving the corrosion resistance of Ni plating on the steel plate for containers is to increase the amount of the chemical conversion coating.
- the chemical conversion treatment with a compound such as Zr, P, Cr, Ti, Mn, and Al is an insulating chemical conversion treatment, the weldability is lowered.
- the steel plate for containers when the amount of Ni plating or chemical conversion treatment film is increased, there is a problem that the manufacturing cost increases.
- the present invention has been made in view of the above problems, and the object of the present invention is to have a Ni-plated steel sheet and a Ni-plated steel sheet that have better corrosion resistance and weldability and are more economical. It is in providing the manufacturing method of.
- the present invention has been made to achieve the above object, and the gist thereof is as follows.
- a first aspect of the present invention is a steel plate, formed on at least one side of the steel plate, formed on the first Ni plating layer containing Ni, and the first Ni plating layer, A Ni-plated steel sheet comprising a second Ni-plated layer.
- the average center line roughness Ra at the interface between the first Ni plating layer and the second Ni plating layer is less than 0.1 ⁇ m, and the average center line roughness Ra of the surface of the second Ni plating layer is 0.1 ⁇ m. is ⁇ 100 [mu] m, the first 1Ni plating layer and Ni deposition amount of the entire first 2Ni plating layer is a single-sided per 20mg / m 2 ⁇ 2500mg / m 2 of metal Ni terms.
- the chlorine content of the first Ni plating layer may be 0 to 100 ppm.
- a chromium oxide, a zirconium compound, a phosphate compound, a titanium oxide, and an aluminum oxide are formed on the second Ni plating layer.
- a chemical conversion treatment film layer containing at least one of manganese oxide is formed on the second Ni plating layer.
- the Ni deposition amount may be per side 400mg / m 2 ⁇ 1000mg / m 2 of metal Ni in terms .
- the Ni adhesion amount of the first Ni plating layer is 300 mg / m 2 to 800 mg / m per side in terms of metallic Ni.
- the Ni deposition amount of the first 2Ni plating layer may be a single-sided per 100mg / m 2 ⁇ 200mg / m 2 of metal Ni terms.
- the surface of the second Ni-plated layer has irregularities whose height difference in the thickness direction of the steel sheet is 1 ⁇ m to 10 ⁇ m. You may have.
- the second aspect of the present invention is Ni ion 5 g / L or more and 60 g / L or less, sulfate ion 20 g / L or more and 300 g / L or less, borate ion 10 g / L or more and 60 g / L or less, and chloride.
- the first Ni plating layer in a second Ni plating bath containing sulfate ions 20 g / L to 300 g / L, borate ions 10 g / L to 60 g / L, and chloride ions 10 g / L to 60 g / L.
- the temperatures of the first Ni plating bath and the second Ni plating bath are 10 ° C. or more and less than 90 ° C., respectively, and in the first plating step and the second plating step, 1.0 A / dm 2 or more and 100 A / dm 2 , respectively.
- the electrolytic treatment is performed in an electrolytic treatment time of 0.2 seconds or more and 150 seconds or less.
- Ni-plated steel sheet having better corrosion resistance and weldability and excellent in economy. Become.
- FIGS. 1A to 2B are explanatory views schematically showing a configuration when the Ni-plated steel sheet according to this embodiment is viewed from the side.
- the Ni-plated steel sheet 10 includes a steel sheet 101, a first Ni-plated layer 103, and a second Ni-plated layer 105, as shown in FIGS. 1A and 1B.
- the first Ni plating layer 103 and the second Ni plating layer 105 may be formed only on one surface of the steel plate 101 as shown in FIG. 1A, or two opposite surfaces of the steel plate 101 as shown in FIG. 1B. It may be formed on one surface.
- the steel plate 101 is used as a base material for the Ni-plated steel plate 10 according to this embodiment.
- the steel plate 101 used in the present embodiment is not particularly limited, and it is possible to use a known steel plate that is usually used as a container material.
- it does not specifically limit about the surface roughness of the steel plate 101, What is necessary is just in the range of the surface roughness of the general steel plate manufactured through the above processes.
- a first Ni plating layer 103 is formed on the surface of the steel plate 101 as shown in FIGS. 1A and 1B.
- the first Ni plating layer 103 is an insoluble Ni plating layer containing Ni (mainly Ni).
- Ni mainly Ni
- a Watt bath mainly composed of Ni ions, sulfate ions, chloride ions and borate ions is well known.
- This first Ni plating layer 103 removes chloride ions from the Watt bath. Formed using a different bath.
- the first Ni plating layer 103 is a Ni plating layer that does not contain chlorine (Cl).
- chloride ions may be contained in the plating bath as long as the content is less than 0.5 g / L. In this case, the first Ni plating layer contains chlorine, but if the chlorine content of the first Ni plating layer is 100 ppm or less, the corrosion resistance and weldability of the Ni plated steel sheet are not affected.
- the first Ni plating layer 103 formed using such a Ni plating bath has an extremely dense surface and has excellent corrosion resistance derived from the dense surface.
- the surface roughness of the first Ni plating layer 103 (in other words, the roughness of the interface between the first Ni plating layer 103 and the second Ni plating layer 105 described later) is less than 0.1 ⁇ m in average centerline roughness Ra.
- the surface roughness Ra of the first Ni plating layer 103 is 0.1 ⁇ m or more, corrosion resistance that can withstand highly corrosive contents cannot be obtained, which is not preferable. Moreover, since the surface roughness Ra of the 1st Ni plating layer 103 is so small that it has the outstanding corrosion resistance, the lower limit is not prescribed
- the second Ni plating layer 105 is a soluble Ni plating layer containing Ni (mainly Ni).
- the second Ni plating layer 105 is formed using a so-called Watt bath containing Ni ions, sulfate ions, chloride ions, and borate ions as main components. Therefore, unlike the first Ni plating layer 103, the second Ni plating layer 105 is a Ni plating layer containing chlorine.
- the surface of the second Ni plating layer 105 formed using the Watt bath has irregularities (that is, average center line roughness) in which the average height h of each irregularity is 0.1 ⁇ m to 100 ⁇ m.
- Ra has irregularities with a thickness of 0.1 ⁇ m to 100 ⁇ m). Since this unevenness is a starting point of energization during welding, it is possible to realize good weldability by providing the second Ni plating layer 105.
- the unevenness is less than 0.1 ⁇ m, the surface of the second Ni plating layer 105 becomes too flat, which is not preferable because the weldability is lowered. Further, when the unevenness exceeds 100 ⁇ m, the appearance is uneven, which is not preferable.
- the irregularities on the surface of the second Ni plating layer 105 are more preferably 1 ⁇ m to 10 ⁇ m.
- the first Ni-plated layer 103 having a dense and flat surface is provided on the surface side of the steel sheet 101, thereby realizing excellent corrosion resistance and a surface with large unevenness.
- Excellent weldability is realized by the second Ni plating layer 105.
- the first Ni plating layer 103 formed under the second Ni plating layer 105 can maintain excellent corrosion resistance. Therefore, in the Ni-plated steel sheet 10 according to the present embodiment, excellent corrosion resistance and weldability can be realized regardless of the surface roughness of the steel sheet 101.
- Ni deposition amount of the total of the first 1Ni plating layer 103 and the 2Ni plating layer 105 is 20mg / m 2 ⁇ 2500mg / m 2 on one surface per metal Ni terms. If the Ni adhesion amount is less than 20 mg / m 2 , it is not preferable because the above corrosion resistance and weldability cannot be realized. On the other hand, when the Ni adhesion amount exceeds 2500 mg / m 2 , the above corrosion resistance and weldability are saturated, which is not economically preferable.
- the first Ni plating layer is 15 mg / m 2 to 2000 mg / m 2 and the second Ni plating layer is 5 mg / m 2 to 500 mg / m 2 in terms of metallic Ni per side.
- the first Ni plating layer adhesion amount is 300 mg / m 2 to 800 mg / m 2
- the second Ni plating layer adhesion amount is 100 mg / m 2 to 200 mg / m 2.
- An economically excellent Ni-plated steel sheet can be realized while maintaining corrosion resistance and weldability.
- the Ni-plated steel sheet 10 according to this embodiment may further include a chemical conversion treatment film layer 107 on the second Ni plating layer 105 as shown in FIGS. 2A and 2B, for example.
- This chemical conversion treatment film layer 107 preferably contains at least one of chromium oxide, zirconium compound, phosphoric acid compound, titanium oxide, aluminum oxide and manganese oxide.
- the method for forming the chemical conversion coating layer 107 is not particularly limited, and known methods such as immersion treatment in the treatment liquid, electrolytic treatment using the treatment liquid, coating treatment using the treatment liquid, and the like depending on the compound to be used. It is possible to use the method.
- the chemical conversion treatment film layer 107 when forming the chemical conversion treatment film layer 107 using a Zr compound, an acidic solution in which Zr ions, fluoride ions, phosphate ions, phenol resins, and the like are dissolved as necessary is used. Then, a chemical conversion treatment film layer 107 containing a Zr compound (more specifically, a Zr oxide), a Zr oxide and a Zr phosphorus is immersed in the acidic solution by immersing the steel sheet or cathodic electrolytic treatment using the acidic solution.
- the chemical conversion treatment film layer 107 containing both of the acid compounds can be formed.
- the chemical conversion treatment film layer 107 using Cr oxide chromate such as sodium salt, potassium salt, ammonium salt of chromic acid, and sulfate ions and fluoride ions are dissolved as necessary. Use an aqueous solution. Then, the chemical conversion treatment film layer 107 containing Cr oxide can be formed by immersing the steel sheet in an aqueous solution or cathodic electrolysis using the aqueous solution.
- the corrosion resistance of the Ni-plated steel sheet 10 can be further improved by further forming the chemical conversion coating layer 107 as described above on the second Ni plating layer 105. Further, when a film layer or a paint layer is further formed on the outermost surface of the Ni-plated steel sheet 10, by forming the chemical conversion treatment film layer 107, between these films and paints and the Ni-plated steel sheet 10 is formed. It becomes possible to improve adhesiveness.
- the adhesion amount of the chemical conversion coating layer 107 is not particularly limited, and may be appropriately determined according to the compound to be used.
- a preferable adhesion amount can be 1 mg / m 2 to 150 mg / m 2 .
- a known treatment agent such as rust preventive oil may be applied to the upper layer of the chemical conversion coating layer 107 as necessary.
- a plating layer using a metal such as Ti, Al, manganese (Mn), or tungsten (W) may be further formed on the second Ni plating layer 105 in place of the chemical conversion treatment film layer 107 described above.
- the surface roughness of the first Ni plating layer 103 can be measured using a known surface roughness measuring machine when the steel sheet passes through the first Ni plating bath for forming the first Ni plating layer 103.
- this known surface roughness measuring instrument needs to have a resolution of 0.1 ⁇ m or less with respect to the centerline roughness Ra.
- the surface roughness of the first Ni plating layer 103 can be measured by the method described below even after the second Ni plating layer 105 is formed. That is, in the Ni-plated steel sheet 10 according to the present embodiment, the first Ni plating layer 103 does not contain chlorine, and the second Ni plating layer 105 contains chlorine. Therefore, analysis using a coaxial cylindrical mirror energy analyzer (Cylindrical Mirror Analyzer: CMA), an electron beam microanalyzer (Electron Probe MicroAnalyzer: EPMA), a fluorescent X-ray analyzer (X-Ray Florescence spectrometer: XRF), etc. By analyzing the chlorine distribution in the Ni plating layer cross section, the interface between the first Ni plating layer 103 and the second Ni plating layer 105 can be specified. Thereafter, the surface roughness of the identified interface can be measured by a known method.
- CMA coaxial cylindrical mirror energy analyzer
- EPMA electron beam microanalyzer
- XRF fluorescent X-ray analyzer
- the surface state (unevenness) of the second Ni plating layer 105 can be measured using a known surface roughness measuring machine.
- this known surface roughness measuring instrument needs to have a resolution of 0.1 ⁇ m to 100 ⁇ m with respect to the center line roughness Ra.
- Ni adhesion amount (metal Ni equivalent amount) can be measured, for example, by the fluorescent X-ray method.
- a calibration curve showing the correlation between the metal Ni equivalent amount and the fluorescent X-ray intensity is specified in advance using a Ni adhesion amount sample whose Ni adhesion amount is known.
- the amount of metal Ni equivalent can be specified.
- the method for measuring the Ni adhesion amount is not limited to the above method, and other known measurement methods can be applied.
- Ni-plated steel sheet 10 has been described in detail above with reference to FIGS. 1A to 3.
- FIG. 4 is a flowchart for explaining an example of the flow of the manufacturing method of the Ni-plated steel sheet according to this embodiment
- FIGS. 5A and 5B are for explaining the method of manufacturing the Ni-plated steel sheet according to this embodiment. It is explanatory drawing of.
- step S101 pretreatment is performed as necessary. That is, depending on the steel plate used as the base material, oil or scales may adhere to the surface of the steel plate 101. Therefore, prior to the Ni plating process described below, a pre-process such as a cleaning process for removing oil and scale on the steel plate 101 is performed.
- a first Ni plating layer 103 is formed on the surface of the steel sheet by electrolytic plating using a first Ni plating bath (step S103).
- a second plating layer 105 is formed on the first Ni plating layer 103 by an electrolytic plating process using a second Ni plating bath (step S105). Details of the components of each Ni plating bath and the electrolytic plating treatment will be described in detail below.
- a chemical conversion treatment film layer 107 is formed on the second Ni plating layer 105 using a known method (step S107).
- post-processing is performed on the manufactured Ni-plated steel sheet 10 as necessary (step S109).
- post-processing For example, the process which apply
- the Ni-plated steel sheet 10 according to the present embodiment is manufactured by performing the processing in such a flow.
- the first Ni plating bath used when forming the first Ni plating layer 103 and the first Ni plating layer 105 used when forming the second Ni plating layer 105 are used.
- Two types of Ni plating baths are used with 2Ni plating baths.
- a first Ni plating bath 201 is provided on the upstream side in the sheet passing direction of the steel sheet, and a second Ni plating bath is provided after the first Ni plating bath 201.
- 203 is provided.
- the first Ni plating bath 201 is a Ni plating bath for forming a dense first Ni plating layer 103 having excellent corrosion resistance on the surface of the steel plate 101 by insoluble Ni plating.
- the first Ni plating bath 201 contains Ni ions 5 g / L to 60 g / L, sulfate ions 20 g / L to 300 g / L, borate ions 10 g / L to 60 g / L, and unavoidable impurities. As is apparent from this bath composition, chloride ions are not added to the first Ni plating bath 201.
- the plating solution is generated using a solvent that does not contain chloride ions, such as ion-exchanged water.
- chloride ions may be contained in the plating bath as long as the content is less than 0.5 g / L.
- the electrode 205 used for an electroplating process is installed so that the steel plate to pass through may be pinched
- the electrode 205 is more insoluble than the Ni anode electrode, such as a titanium (Ti) -platinum (Pt) electrode, a lead dioxide (PbO 2 ) electrode, a lead (Pb) -tin (Sn) -silver (Ag) electrode, etc. It is desirable to use electrodes.
- the insoluble electrode is superior to the Ni anode electrode in that the uniformity of Ni plating is improved.
- Ni anode electrode When a Ni anode electrode is used for the electroplating process, a relatively large Ni lump may be released in the bath during electrolysis, and may be sandwiched between the sink roll and the steel plate, resulting in a push. In particular, the formation of the first Ni plating layer requires a dense and smooth surface, and such a pressing rod is fatal in terms of quality. On the other hand, an insoluble electrode is free from wrinkles and Ni ions can be present almost uniformly in the bath, so that uniform plating with excellent corrosion resistance is easily formed.
- the bath temperature of the first Ni plating bath 201 is, for example, 10 ° C. or more and less than 90 ° C. When the bath temperature is less than 10 ° C., the Ni deposition efficiency decreases, which is not preferable. Further, when the bath temperature is 90 ° C. or higher, the unevenness of the Ni plating becomes uneven, which is not preferable.
- the bath temperature of the first Ni plating bath 201 is more preferably 20 ° C. or higher and lower than 30 ° C.
- the electrolytic plating process is performed under the conditions of a current density of 1.0 A / dm 2 or more and 100 A / dm 2 or less and an electrolytic treatment time of 0.2 seconds or more and 150 seconds or less.
- a current density 1.0 A / dm 2 or more and 100 A / dm 2 or less
- an electrolytic treatment time 0.2 seconds or more and 150 seconds or less.
- the current density of the first Ni plating bath 201 is more preferably 5 A / dm 2 or more and 10 A / dm 2 or less.
- the electrolytic treatment time of the first Ni plating bath 201 is more preferably 0.3 seconds or more and 50 seconds or less, and further preferably 0.5 seconds or more and 6 seconds or less.
- the second Ni plating bath 203 is a Ni plating bath for forming the second Ni plating layer 105 having large irregularities on the surface of the first Ni plating layer 103 by soluble Ni plating.
- This second Ni plating bath 203 is composed of Ni ions 5 g / L to 60 g / L, sulfate ions 20 g / L to 300 g / L, borate ions 10 g / L to 60 g / L, chloride ions 10 g / L to 60 g. / L or less and inevitable impurities are included.
- chloride ions coordinate with Ni ions present in the bath to form a complex.
- the formed second Ni plating layer 105 is a plating layer containing chlorine.
- chlorine ions contained in the complex during electrolysis inhibit uniform formation of Ni plating. For this reason, the 2nd Ni plating layer 105 to be formed is formed with large unevenness with good weldability.
- an electrode 207 used for the electrolytic plating process is installed so as to sandwich a steel plate to be passed therethrough.
- the electrode 207 it is possible to use an insoluble electrode such as a Ti—Pt electrode similarly to the electrode 205 in the first Ni plating bath 201.
- an insoluble electrode such as a Ti—Pt electrode
- chlorine gas harmful to the human body is generated in the vicinity of the electrode due to a reaction of 2Cl ⁇ ⁇ Cl 2 + e ⁇ , and therefore an exhaust system for exhausting chlorine gas Is required. Therefore, it is preferable to use a Ni anode electrode as the electrode 207 in the second Ni plating bath 203.
- Ni anode electrode Ni ions are eluted by the reaction of Ni ⁇ Ni 2+ + 2e ⁇ . In this case, since chlorine gas is not generated, there is no need to provide an exhaust facility.
- the bath temperature of the second Ni plating bath 203 is, for example, 10 ° C. or more and less than 90 ° C. When the bath temperature is less than 10 ° C., the Ni deposition efficiency decreases, which is not preferable. Further, when the bath temperature is 90 ° C. or higher, the unevenness of the Ni plating becomes uneven, which is not preferable.
- the bath temperature of the second Ni plating bath 203 is more preferably 70 ° C. or higher and lower than 80 ° C.
- the electrolytic plating process is performed under the conditions of a current density of 1.0 A / dm 2 or more and 100 A / dm 2 or less and an electrolytic treatment time of 0.2 seconds or more and 150 seconds or less.
- a current density 1.0 A / dm 2 or more and 100 A / dm 2 or less
- an electrolytic treatment time 0.2 seconds or more and 150 seconds or less.
- the current density of the second Ni plating bath 203 is more preferably 60 A / dm 2 or more and 70 A / dm 2 or less.
- the electrolytic treatment time of the second Ni plating bath 203 is more preferably 0.3 seconds or more and 50 seconds or less, and further preferably 0.5 seconds or more and 6 seconds or less.
- the second plating step using the second Ni plating bath 203 is continuously performed after the first plating step using the first Ni plating bath 201. Done. Since the plating steps are performed in this order, chloride ions contained in the second Ni plating bath 203 are not mixed into the first Ni plating bath 201. Moreover, as shown to FIG. 5A, it is not necessary to provide the rinse process which rinses the surface of a steel plate between a 1st plating process and a 2nd plating process. Needless to say, a rinsing bath 209 may be provided between the first Ni plating bath 201 and the second Ni plating bath 203, as shown in FIG. 5B.
- 5A and 5B illustrate the case where the first Ni plating bath 201 and the second Ni plating bath 203 have a two-pass configuration, the number of passes in the plating bath is not limited to the illustrated example, and There may be a large number of passes.
- 5A and 5B illustrate the case where each of the first Ni plating bath 201 and the second Ni plating bath 203 is provided one by one. However, there are a plurality of the first Ni plating bath 201 and the second Ni plating bath 203. You may be comprised with the tank of this.
- the Ni-plated steel sheet and the method for producing the Ni-plated steel sheet according to the present invention will be specifically described with reference to Examples and Comparative Examples.
- the Example shown below is an example of the manufacturing method of the Ni plating steel plate and Ni plating steel plate which concern on this invention.
- the manufacturing method of the Ni-plated steel sheet and the Ni-plated steel sheet according to the present invention is not limited to the following examples.
- Ni plating conditions Using the two types of Ni plating baths described in Tables 1 and 3 to 5, Ni plated steel sheets were produced.
- the conditions described in the “First Ni plating electrolysis conditions” column are the conditions relating to the first Ni plating bath 201 and are described in the “Second Ni plating electrolysis conditions” column. These conditions are conditions relating to the second Ni plating bath 203.
- each experimental example shown in Table 1 and Table 2 was conducted by paying attention mainly to the characteristics of the Ni-plated steel sheet produced, and each experimental example shown in Table 3 and Table 4 is The experiment was conducted while further changing the Ni plating bath used for the production of the Ni plated steel sheet.
- Each experimental example shown in Table 5 and Table 6 is an experiment in which the amount of Ni deposition is changed by changing the energization time in the electrolytic treatment.
- Ni-plated steel sheets produced under the conditions described in Tables 1 to 6 were evaluated by the following evaluation methods.
- the amount of metallic Ni shown in Tables 2 and 6 was measured with a fluorescent X-ray adhesion meter, and average centerline roughness Ra and second Ni at the interface between the first Ni plating layer 103 and the second Ni plating layer 105 were measured.
- the average center line roughness Ra on the surface of the plating layer 105 was measured by a stylus type surface roughness measuring instrument.
- Tables 3 and 4 do not show the measurement results of the amount of metallic Ni and the two types of average centerline roughness Ra. However, in each level shown in Tables 3 and 4, those corresponding to the examples are also shown. The results are included in the range of the metal Ni amount and the average centerline roughness corresponding to the Ni-plated steel sheet according to the present invention.
- the corrosion resistance test solution As the corrosion resistance test solution, 3% acetic acid was used.
- the Ni-plated steel sheets shown in Table 1 and Tables 3 to 5 were cut into a diameter of 35 mm, and fixed on the mouth of a heat-resistant bottle containing a corrosion resistance test solution. Thereafter, heat treatment was performed at 121 ° C. for 60 minutes. After the heat treatment, the corrosion resistance was evaluated by the ratio of the corroded area to the area where the corrosion resistance test solution touches the Ni-plated steel sheet. More specifically, a score of 1 to 10 points was given by the ratio of the corrosion area to the area where the test piece comes into contact with the test solution. In this corrosion resistance test, when the score is 5 points or more, it can be used as a steel plate for containers.
- Corrosion resistance evaluation items in Table 2 to Table 4 and Table 6 are “Very Good” for 10 to 9 points, “Good” for 8 to 7 points, “Fair” for 6 to 5 points, 4 points or less Was labeled “Poor”.
- Ni-plated steel plate having better corrosion resistance and weldability and excellent in economy.
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Abstract
Description
本願は、2013年4月30日に、日本に出願された特願2013-95785号に基づき優先権を主張し、その内容をここに援用する。
特許文献4に記載のNiめっき鋼板は、Niめっき層の形成にいわゆるワット浴を用いており、ワット浴を使用したNiめっきでは、Niめっき量を増加させたとしても表面の凹凸が粗大になるだけで緻密な皮膜は形成されず、皮膜欠陥の存在により耐食性は向上しない。また、塩化物イオンを含まないワット浴により形成されたNiめっきは緻密であるものの、表面の凹凸が少ないため、溶接性が低下してしまう。
このように、従来の方法では、耐食性と溶接性とを両立させることは困難であった。
また、容器用鋼板において、Niめっきや化成処理皮膜の量を増加させた場合、製造コストが上昇してしまうという問題があった。
(2)上記(1)に記載のNiめっき鋼板では、前記第1Niめっき層の塩素の含有量は、0~100ppmであってもよい。
(3)上記(1)または(2)に記載のNiめっき鋼板は、前記第1Niめっき層のNi付着量が、金属Ni換算で片面当たり15mg/m2~2000mg/m2であり、前記第2Niめっき層のNi付着量は、金属Ni換算で片面当たり5mg/m2~500mg/m2であってもよい。
(4)上記(1)~(3)の何れか一項に記載のNiめっき鋼板では、前記第2Niめっき層上に、クロム酸化物、ジルコニウム化合物、リン酸化合物、チタン酸化物、アルミ酸化物及びマンガン酸化物、の少なくとも一種を含む化成処理皮膜層を更に備えていてもよい。
(5)上記(1)~(4)の何れか一項に記載のNiめっき鋼板では、前記Ni付着量は、金属Ni換算で片面当たり400mg/m2~1000mg/m2であってもよい。
(6)上記(1)~(5)の何れか一項に記載のNiめっき鋼板では、前記第1Niめっき層の前記Ni付着量は、金属Ni換算で片面当たり300mg/m2~800mg/m2であり、前記第2Niめっき層の前記Ni付着量は、金属Ni換算で片面当たり100mg/m2~200mg/m2であってもよい。
(7)上記(1)~(6)の何れか一項に記載のNiめっき鋼板では、前記第2Niめっき層の表面は、前記鋼板の厚さ方向での高低差が1μm~10μmである凹凸を有していてもよい。
(8)本発明の第二の態様は、Niイオン5g/L以上60g/L以下、硫酸イオン20g/L以上300g/L以下、ホウ酸イオン10g/L以上60g/L以下、及び、塩化物イオン0.5g/L未満を含む第1Niめっき浴中で鋼板を電解処理して、当該鋼板上に第1Niめっき層を形成する第1めっき工程と、Niイオン5g/L以上60g/L以下、硫酸イオン20g/L以上300g/L以下、ホウ酸イオン10g/L以上60g/L以下、及び、塩化物イオン10g/L以上60g/L以下を含む第2Niめっき浴中で前記第1Niめっき層の形成された前記鋼板を電解処理して、当該第1Niめっき層上に第2Niめっき層を形成する第2めっき工程と、を含むNiめっき鋼板の製造方法である。前記第1Niめっき浴及び前記第2Niめっき浴の温度は、それぞれ10℃以上90℃未満であり、前記第1めっき工程及び前記第2めっき工程では、それぞれ1.0A/dm2以上100A/dm2以下の電流密度により、0.2秒以上150秒以下の電解処理時間で、前記電解処理が行われる。
(9)上記(8)に記載のNiめっき鋼板の製造方法では、前記第1めっき工程と前記第2めっき工程との間に、リンス工程を設けなくてもよい。
まず、図1A~図2Bを参照しながら、本発明の実施形態に係るNiめっき鋼板の構成について詳細に説明する。図1A~図2Bは、本実施形態に係るNiめっき鋼板を側方から見た場合の構成について模式的に示した説明図である。
鋼板101は、本実施形態に係るNiめっき鋼板10の母材として用いられる。本実施形態で用いられる鋼板101については特に限定されるものではなく、通常、容器材料として用いられる公知の鋼板を使用することが可能である。この公知の鋼板の製造方法や材質についても特に限定されるものではなく、通常の鋼片製造工程から、熱間圧延、酸洗、冷間圧延、焼鈍、調質圧延等の公知の工程を経て製造されたものでよい。また、鋼板101の表面粗度については特に限定されるものではなく、上記のような工程を経て製造される一般的な鋼板の表面粗度の範囲内であればよい。
鋼板101の表面上には、図1A及び図1Bに示したように、第1Niめっき層103が形成される。第1Niめっき層103は、Niを含有する(Niを主体とする)、不溶性Niめっき層である。電気ニッケルめっき浴としてはNiイオン、硫酸イオン、塩化物イオン及びホウ酸イオンを主成分とするワット浴がよく知られているが、この第1Niめっき層103は、ワット浴から塩化物イオンを除いた浴を用いて形成される。従って、第1Niめっき層103は、塩素(Cl)を含有しないNiめっき層となる。ただし、めっき浴中に0.5g/L未満の含有量であれば塩化物イオンを含んでいてもよい。この場合には、第1Niめっき層が塩素を含有することとなるが、第1Niめっき層の塩素含有量が100ppm以下であれば、Niめっき鋼板の耐食性や溶接性には影響がない。
第1Niめっき層103上には、図1A及び図1Bに示したように、第2Niめっき層105が形成される。第2Niめっき層105は、Niを含有する(Niを主体とする)、可溶性Niめっき層である。この第2Niめっき層105は、Niイオン、硫酸イオン、塩化物イオン及びホウ酸イオンを主成分とするいわゆるワット浴を用いて形成される。従って、第2Niめっき層105は、第1Niめっき層103とは異なり、塩素を含有するNiめっき層となる。
本実施形態に係るNiめっき鋼板10において、第1Niめっき層103と第2Niめっき層105との合計のNi付着量は、片面当たり金属Ni換算で20mg/m2~2500mg/m2である。Ni付着量が20mg/m2未満である場合、上記のような耐食性及び溶接性を実現することができないため、好ましくない。また、Ni付着量が2500mg/m2を超過している場合、上記のような耐食性及び溶接性が飽和するため経済的に好ましくない。
特に、片面当たり金属Ni換算で第1Niめっき層が15mg/m2~2000mg/m2、第2Niめっき層が5mg/m2~500mg/m2の組み合わせであるときに、優れた耐食性及び溶接性を実現することができる。
なお、第1Niめっき層103と第2Niめっき層105との合計のNi付着量を、片面当たり400mg/m2~1000mg/m2とすることで、より好ましい結果が得られる。この場合、第1Niめっき層の付着量が300mg/m2~800mg/m2、第2Niめっき層の付着量が100mg/m2~200mg/m2となるように組み合わせることで、上記のような耐食性及び溶接性を維持しつつ、経済的にも優れたNiめっき鋼板を実現することができる。
本実施形態に係るNiめっき鋼板10は、例えば図2A及び図2Bに示したように、第2Niめっき層105上に更に化成処理皮膜層107を有していても良い。この化成処理皮膜層107は、クロム酸化物、ジルコニウム化合物、リン酸化合物、チタン酸化物、アルミ酸化物及びマンガン酸化物の少なくとも一種を含むことが好ましい。化成処理皮膜層107の形成方法については特に限定されるものではなく、用いる化合物に応じて、処理液への浸漬処理、処理液を用いた電解処理、処理液を利用した塗布処理等といった公知の方法を利用することが可能である。
次に、各Niめっき層の表面状態の測定方法について説明する。
第1Niめっき層103の表面粗度は、第1Niめっき層103を形成するための第1Niめっき浴を鋼板が通過したときに、公知の表面粗度測定機を用いて測定することが可能である。ここで、この公知の表面粗度測定機は、中心線粗度Raに関して、0.1μm以下の分解能を有することが必要である。
次に、第1Niめっき層103及び第2Niめっき層105のNi付着量の測定方法について説明する。
Ni付着量(金属Ni換算量)は、例えば、蛍光X線法により測定することが可能である。この場合、Ni付着量が既知であるNi付着量サンプルを利用して金属Ni換算量と蛍光X線強度との相関関係を示した検量線を予め特定しておき、この検量線を用いて相対的に金属Ni換算量を特定することができる。
次に、図4~図5Bを参照しながら、本実施形態に係るNiめっき鋼板10の製造方法について、詳細に説明する。図4は、本実施形態に係るNiめっき鋼板の製造方法の流れの一例について説明するための流れ図であり、図5A及び図5Bは、本実施形態に係るNiめっき鋼板の製造方法について説明するための説明図である。
本実施形態に係るNiめっき鋼板10の製造方法では、まず、必要に応じて前処理が実施される(ステップS101)。すなわち、母材として用いる鋼板によっては、鋼板101の表面に油分やスケール等が付着している場合がある。そこで、以下で説明するNiめっき処理に先立って、鋼板101上の油分やスケールを除去する洗浄処理等の前処理が実施される。
次に、図5A及び図5Bを参照しながら、2種類のNiめっき浴を用いた電解めっき処理について、詳細に説明する。
不溶性電極は、Niアノード電極よりもNiめっきの均一性が向上する点において優れている。電解めっき処理にNiアノード電極を用いた場合、電解中に比較的大きなNiの塊が浴中に遊離し、シンクロールと鋼板の間に挟まれて、押し疵になるおそれがある。特に第1Niめっき層の形成では、緻密で平滑な表面が要求されるため、このような押し疵は、品質面において致命的となる。一方、不溶性電極では押し疵の心配がなく、Niイオンを浴中にほぼ均一に存在させることが可能となるため、耐食性に優れた均一なめっきが形成されやすい。
電流密度が1.0A/dm2未満である場合には、Ni付着効率が低下するため好ましくない。一方、電流密度が100A/dm2を超過する場合には、Niめっきの凹凸が不均一となるため好ましくない。第1Niめっき浴201の電流密度は、より好ましくは5A/dm2以上10A/dm2以下である。
また、電解処理時間が0.2秒未満である場合には、必要なNi付着量を得ることが困難であるため好ましくない。一方、電解処理時間が150秒を超過する場合には、Ni付着量が多すぎるため好ましくない。第1Niめっき浴201の電解処理時間は、より好ましくは0.3秒以上50秒以下、さらに好ましくは0.5秒以上6秒以下である。
電流密度が1.0A/dm2未満である場合には、Ni付着効率が低下するため好ましくない。一方、電流密度が100A/dm2を超過する場合には、Niめっきの凹凸が不均一となるため好ましくない。第2Niめっき浴203の電流密度は、より好ましくは60A/dm2以上70A/dm2以下である。
また、電解処理時間が0.2秒未満である場合には、必要なNi付着量を得ることが困難であるため好ましくない。一方、電解処理時間が150秒を超過する場合には、Ni付着量が多すぎるため好ましくない。第2Niめっき浴203の電解処理時間は、より好ましくは0.3秒以上50秒以下、さらに好ましくは0.5秒以上6秒以下である。
また、図5Aに示したように、第1めっき工程と第2めっき工程との間には、鋼板の表面をリンスするリンス工程を設けなくとも良い。なお、図5Bに示したように、第1Niめっき浴201と第2Niめっき浴203との間に、リンス浴209を設けても良いことは、言うまでもない。
図5A及び図5Bでは、各第1Niめっき浴201及び第2Niめっき浴203がそれぞれ1槽ずつ設けられている場合について図示しているが、第1Niめっき浴201及び第2Niめっき浴203は、複数の槽で構成されていてもよい。
(1)Niめっき条件
表1、表3~表5に記載した2種類のNiめっき浴を利用して、Niめっき鋼板をそれぞれ製造した。表1、表3~表5において、「第1Niめっき電解条件」の欄に記載されている条件が、第1Niめっき浴201に関する条件であり、「第2Niめっき電解条件」の欄に記載されている条件が、第2Niめっき浴203に関する条件である。
なお、表1~表6の備考欄に、本発明の実施例に該当する水準には実施例と、本発明の範囲外の水準には比較欄と記載した。
本実施例では、表1、表3~表5に示した条件で製造したNiめっき鋼板について、耐食性及び溶接性に着目して評価を行った。
耐食性試験液には、3%酢酸を用いた。表1、表3~表5に示したNiめっき鋼板をφ35mmに切り出して、耐食性試験液を入れた耐熱瓶の口に乗せて固定した。その後、121℃で60分の熱処理を行った。熱処理後、耐食性試験液がNiめっき鋼板に触れる面積に対する、腐食した面積の割合により耐食性を評価した。より詳細には、試験片が試験液と接触する面積に対する腐食面積の割合で、1~10点の評点をつけた。この耐食性試験において、評点が5点以上の場合、容器用鋼板として使用することが可能である。
9点:90%未満~80%以上
8点:80%未満~70%以上
7点:70%未満~60%以上
6点:60%未満~50%以上
5点:50%未満~40%以上
4点:40%未満~30%以上
3点:30%未満~20%以上
2点:20%未満~10%以上
1点:10%未満~0%以上
溶接性は、スードロニック社製の飲料缶用溶接機を用いて、溶接個所に発生するチリ(溶接個所から1mm程度はみ出した鋼板の塊)の発生の有無で溶接の良、不良を判断した。チリが発生していない場合を「Good」とし、チリが発生した場合「Bad」とした。
101 鋼板
103 第1Niめっき層
105 第2Niめっき層
107 化成処理皮膜層
201 第1Niめっき浴
203 第2Niめっき浴
205,207 電極
209 リンス浴
Claims (9)
- 鋼板と、
前記鋼板の少なくとも片面に形成されており、Niを含有する第1Niめっき層と、
前記第1Niめっき層上に形成されており、Niを含有する第2Niめっき層と、
を備え、
前記第1Niめっき層と前記第2Niめっき層との界面での平均中心線粗度Raは、0.1μm未満であり、
前記第2Niめっき層の表面の平均中心線粗度Raは、0.1μm~100μmであり、
前記第1Niめっき層及び前記第2Niめっき層全体のNi付着量は、金属Ni換算で片面当たり20mg/m2~2500mg/m2である
ことを特徴とする、Niめっき鋼板。 - 前記第1Niめっき層の塩素の含有量は、0~100ppmである
ことを特徴とする、請求項1に記載のNiめっき鋼板。 - 前記第1Niめっき層のNi付着量は、金属Ni換算で片面当たり15mg/m2~2000mg/m2であり、
前記第2Niめっき層のNi付着量は、金属Ni換算で片面当たり5mg/m2~500mg/m2である
ことを特徴とする、請求項1または2に記載のNiめっき鋼板。 - 前記第2Niめっき層上に、クロム酸化物、ジルコニウム化合物、リン酸化合物、チタン酸化物、アルミ酸化物及びマンガン酸化物、の少なくとも一種を含む化成処理皮膜層を更に備える
ことを特徴とする、請求項1~3の何れか1項に記載のNiめっき鋼板。 - 前記Ni付着量は、金属Ni換算で片面当たり400mg/m2~1000mg/m2である
ことを特徴とする、請求項1~4の何れか1項に記載のNiめっき鋼板。 - 前記第1Niめっき層の前記Ni付着量は、金属Ni換算で片面当たり300mg/m2~800mg/m2であり、
前記第2Niめっき層の前記Ni付着量は、金属Ni換算で片面当たり100mg/m2~200mg/m2である
ことを特徴とする、請求項1~5の何れか1項に記載のNiめっき鋼板。 - 前記第2Niめっき層の表面は、前記鋼板の厚さ方向での平均高低差が1μm~10μmである凹凸を有している
ことを特徴とする、請求項1~6の何れか1項に記載のNiめっき鋼板。 - Niイオン5g/L以上60g/L以下、硫酸イオン20g/L以上300g/L以下、ホウ酸イオン10g/L以上60g/L以下、及び、塩化物イオン0.5g/L未満を含む第1Niめっき浴中で鋼板を電解処理して、当該鋼板上に第1Niめっき層を形成する第1めっき工程と、
Niイオン5g/L以上60g/L以下、硫酸イオン20g/L以上300g/L以下、ホウ酸イオン10g/L以上60g/L以下、及び、塩化物イオン10g/L以上60g/L以下を含む第2Niめっき浴中で前記第1Niめっき層の形成された前記鋼板を電解処理して、当該第1Niめっき層上に第2Niめっき層を形成する第2めっき工程と、
を含み、
前記第1Niめっき浴及び前記第2Niめっき浴の温度は、それぞれ10℃以上90℃未満であり、
前記第1めっき工程及び前記第2めっき工程では、それぞれ1.0A/dm2以上100A/dm2以下の電流密度により、0.2秒以上150秒以下の電解処理時間で、前記電解処理が行われる
ことを特徴とする、Niめっき鋼板の製造方法。 - 前記第1めっき工程と前記第2めっき工程との間に、リンス工程を設けない
ことを特徴とする、請求項8に記載のNiめっき鋼板の製造方法。
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US14/787,498 US10190231B2 (en) | 2013-04-30 | 2014-04-30 | Ni-plated steel sheet, and method for producing Ni-plated steel sheet |
CN201480024785.4A CN105164321B (zh) | 2013-04-30 | 2014-04-30 | 镀镍钢板以及镀镍钢板的制造方法 |
EP14791996.3A EP2993257B8 (en) | 2013-04-30 | 2014-04-30 | Ni-plated steel sheet and method for producing ni-plated steel sheet |
JP2015514862A JP5884947B2 (ja) | 2013-04-30 | 2014-04-30 | Niめっき鋼板及びNiめっき鋼板の製造方法 |
KR1020157030721A KR101708141B1 (ko) | 2013-04-30 | 2014-04-30 | Ni 도금 강판 및 Ni 도금 강판의 제조 방법 |
ES14791996T ES2736288T3 (es) | 2013-04-30 | 2014-04-30 | Lámina de acero chapada en Ni y método para producir lámina de acero chapada en Ni |
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CN (1) | CN105164321B (ja) |
ES (1) | ES2736288T3 (ja) |
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JP2019104948A (ja) * | 2017-12-08 | 2019-06-27 | 東洋鋼鈑株式会社 | 表面処理鋼板およびその製造方法 |
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WO2020137874A1 (ja) * | 2018-12-27 | 2020-07-02 | 日本製鉄株式会社 | 加工後耐食性に優れたNiめっき鋼板、及びNiめっき鋼板の製造方法 |
JPWO2020137874A1 (ja) * | 2018-12-27 | 2021-02-18 | 日本製鉄株式会社 | 加工後耐食性に優れたNiめっき鋼板、及びNiめっき鋼板の製造方法 |
CN113166966A (zh) * | 2018-12-27 | 2021-07-23 | 日本制铁株式会社 | 加工后耐腐蚀性优异的镀镍钢板及镀镍钢板的制造方法 |
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CN105164321A (zh) | 2015-12-16 |
MY176155A (en) | 2020-07-24 |
TW201500179A (zh) | 2015-01-01 |
EP2993257A4 (en) | 2016-12-14 |
JP5884947B2 (ja) | 2016-03-15 |
KR101708141B1 (ko) | 2017-02-17 |
KR20150136107A (ko) | 2015-12-04 |
CN105164321B (zh) | 2017-10-31 |
EP2993257B8 (en) | 2019-08-21 |
JPWO2014178396A1 (ja) | 2017-02-23 |
EP2993257B1 (en) | 2019-06-05 |
US10190231B2 (en) | 2019-01-29 |
TWI510362B (zh) | 2015-12-01 |
ES2736288T3 (es) | 2019-12-27 |
US20160102414A1 (en) | 2016-04-14 |
EP2993257A1 (en) | 2016-03-09 |
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