WO2025004426A1 - Tôle d'acier traitée en surface et procédé de fabrication associé - Google Patents

Tôle d'acier traitée en surface et procédé de fabrication associé Download PDF

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Publication number
WO2025004426A1
WO2025004426A1 PCT/JP2024/003164 JP2024003164W WO2025004426A1 WO 2025004426 A1 WO2025004426 A1 WO 2025004426A1 JP 2024003164 W JP2024003164 W JP 2024003164W WO 2025004426 A1 WO2025004426 A1 WO 2025004426A1
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Prior art keywords
chromium
steel sheet
containing layer
treated steel
oxygen
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PCT/JP2024/003164
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English (en)
Japanese (ja)
Inventor
卓嗣 植野
方成 友澤
祐介 中川
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JFE Steel Corp
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JFE Steel Corp
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Priority to JP2024527467A priority Critical patent/JP7552960B1/ja
Priority to KR1020257027930A priority patent/KR20250138771A/ko
Priority to EP24831307.4A priority patent/EP4667626A1/fr
Priority to CN202480042543.1A priority patent/CN121399303A/zh
Publication of WO2025004426A1 publication Critical patent/WO2025004426A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/38—Chromatising
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • C25D9/10—Electrolytic coating other than with metals with inorganic materials by cathodic processes on iron or steel

Definitions

  • the present invention relates to a surface-treated steel sheet, and in particular to a surface-treated steel sheet having excellent corrosion resistance in a BPA (bisphenol A)-free painted area.
  • the surface-treated steel sheet of the present invention can be suitably used for containers such as cans.
  • the present invention also relates to a method for manufacturing the surface-treated steel sheet.
  • tinplate Sn-plated steel sheet
  • TFS tin-free steel sheet
  • Tinplate and TFS are used with an organic resin coating such as epoxy paint or PET film to accommodate a variety of contents.
  • an organic resin coating such as epoxy paint or PET film
  • the steel plate is electrolytically treated or immersed in an aqueous solution containing hexavalent Cr to form a chromium oxide layer on the outermost surface, which provides excellent adhesion to the organic resin coating layer.
  • the deformation of the organic resin coating layer follows the deformation of the steel plate that accompanies can manufacturing, ensuring corrosion resistance to a variety of contents even after can manufacturing.
  • Patent Documents 3 to 6 are known as methods for forming surface-treated steel sheets without using hexavalent chromium.
  • a surface treatment layer is formed by electrolytic treatment in an electrolyte solution containing a trivalent chromium compound such as basic chromium sulfate.
  • Patent Documents 3 to 6 make it possible to form a surface treatment layer without using hexavalent chromium. Furthermore, Patent Documents 3 to 6 show that the above methods can produce a surface-treated steel sheet that has excellent adhesion to epoxy-based paint. Furthermore, Patent Documents 3 and 4 show that a surface-treated steel sheet that exhibits excellent corrosion resistance even after being coated with epoxy-based paint and deformed can be obtained.
  • the present invention was made in consideration of the above situation, and its purpose is to provide a surface-treated steel sheet that can be manufactured without using hexavalent chromium and has excellent corrosion resistance in the BPA-free painted area.
  • the inventors of the present invention conducted extensive research to achieve the above objective, and as a result, have come to the following findings (1) and (2).
  • the above-mentioned surface-treated steel sheet can be produced by contacting a steel sheet with an aqueous solution containing sulfate ions, holding the aqueous solution on the surface of the steel sheet in a state in which more than 30.0 g/ m2 and not more than 60.0 g/ m2 is present for 0.10 to 20.0 seconds, and then subjecting the steel sheet to cathodic electrolysis in an electrolytic solution containing 0.05 mol/L or more of trivalent chromium ions.
  • the present invention was completed based on the above findings.
  • the gist of the present invention is as follows:
  • a steel plate A surface-treated steel sheet comprising a chromium-containing layer disposed on at least one surface of the steel sheet, an oxygen-enriched region containing O at an atomic concentration of 10% or more is present in the vicinity of the interface between the steel sheet and the chromium-containing layer, The vicinity is a region in which the atomic ratio of Fe to Cr is in the range of 0.7 to 1.3.
  • a method for producing a surface-treated steel sheet comprising a steel sheet and a chromium-containing layer disposed on at least one surface of the steel sheet, comprising the steps of: a steel sheet surface conditioning step of contacting the steel sheet with an aqueous solution containing sulfate ions and holding the aqueous solution on the surface of the steel sheet in an amount of more than 30.0 g/ m2 and not more than 60.0 g/ m2 for 0.10 to 20.0 seconds; and a cathodic electrolysis step of cathodic electrolysis of the steel sheet in an electrolytic solution containing 0.05 mol/L or more of trivalent chromium ions.
  • the present invention it is possible to provide a surface-treated steel sheet that has excellent corrosion resistance in the BPA-free painted area without using hexavalent chromium.
  • the surface-treated steel sheet of the present invention can be suitably used as a material for containers, etc.
  • the surface-treated steel sheet is a surface-treated steel sheet having a chromium-containing layer on at least one side of the steel sheet.
  • the steel sheet is not particularly limited and any steel sheet can be used, but it is preferable to use a steel sheet for cans.
  • the steel sheet can be, for example, an ultra-low carbon steel sheet or a low carbon steel sheet.
  • the manufacturing method of the steel sheet is also not particularly limited and any steel sheet manufactured by any method can be used, but usually a cold-rolled steel sheet can be used.
  • the cold-rolled steel sheet can be manufactured by a general manufacturing process that includes, for example, hot rolling, pickling, cold rolling, annealing, and temper rolling.
  • the composition of the steel plate is not particularly limited, but may contain C, Mn, P, S, Si, Cu, Ni, Mo, Al, and unavoidable impurities within a range that does not impair the effects of the present invention.
  • the steel plate may preferably have a composition as specified in ASTM A623M-09, for example.
  • C 0.0001 to 0.13%
  • Si 0 to 0.020%
  • Mn 0.01 to 0.70%
  • P 0 to 0.15%
  • S 0 to 0.050%
  • Al 0-0.20%
  • N 0 to 0.040%
  • Cu 0 to 0.20%
  • Cr 0 to 0.10%
  • Mo 0 to 0.05%
  • Ti 0 to 0.020%
  • Nb 0 to 0.020%
  • B 0 to 0.020%
  • Ca 0-0.020%
  • Sn 0 to 0.020%
  • Sb 0 to 0.020%
  • the balance being Fe and unavoidable impurities.
  • the lower the content of Si, P, S, Al, and N the more preferable the components are, and Cu, Ni, Cr, Mo, Ti, Nb, B, Ca, Sn, and Sb are components that may be added as desired.
  • the thickness of the steel plate is not particularly limited, but is preferably 0.60 mm or less. On the other hand, the lower limit of the thickness is also not particularly limited, but is preferably 0.10 mm or more. Note that “steel plate” is defined here to include “steel strip.”
  • a chromium-containing layer is present on at least one surface of the steel sheet.
  • the components constituting the chromium-containing layer are not particularly limited, but may include metallic chromium and a chromium compound.
  • the chromium compound may include any chromium compound without being particularly limited.
  • the chromium compound may include, for example, at least one selected from the group consisting of chromium oxide, chromium carbide, chromium sulfide, chromium nitride, chromium chloride, chromium bromide, and chromium boride.
  • the chromium-containing layer may contain impurities in addition to the metallic chromium and the chromium compound.
  • the impurities include metal elements such as Ni, Cu, Sn, and Zn that are mixed as impurities in the electrolytic solution described below.
  • the metal elements are typically considered to exist in the chromium-containing layer in a metallic state, but may also exist as compounds.
  • the chromium-containing layer preferably has a total content of elements constituting metallic chromium and chromium compounds of 90 atomic % or more.
  • the total content is expressed as a percentage of the ratio of the total atomic number of elements constituting metallic chromium and chromium compounds to the total atomic number of all elements other than Fe.
  • the total content can be determined by measuring the content (atomic %) of each of the elements constituting the chromium compound and the metallic chromium contained in the chromium-containing layer by X-ray photoelectron spectroscopy (XPS) and adding them up.
  • XPS X-ray photoelectron spectroscopy
  • the content (atomic ratio) of each element can be calculated by the relative sensitivity coefficient method from the integrated intensity of the peak corresponding to each element.
  • the content of chromium carbide can be determined from the integrated intensity of the C 1s carbide peak appearing near 281.0 eV.
  • the C content atomic ratio to the total of all elements other than Fe
  • the Cr2O3 content can be determined from the integrated intensity of the Cr 2p oxide peak appearing near 576.7 eV. Also, the CrO3 content can be determined from the integrated intensity of the Cr 2p oxide peak appearing near 579.2 eV.
  • Chromium sulfide S 2p sulfide peak appearing around 162.3 eV
  • Chromium nitride CrN
  • Chromium chloride CrCl3
  • Chromium bromide CrBr3
  • Br 3d peak appearing around 69.1 eV
  • Chromium boride CrB: Br 1s peak appearing around 188.2 eV
  • the metallic chromium content is calculated from the integrated intensity of the Cr 2p peak that appears around 573.8 eV, and is then calculated by subtracting the content of Cr atoms contained as chromium compounds from the chromium content.
  • the total content of metallic chromium and the elements that make up the chromium compound can be calculated by adding together the content of metallic chromium obtained by the above method and the content of each element that makes up the chromium compound.
  • the total content refers to the value at the midpoint of the thickness of the chromium-containing layer.
  • the midpoint can be determined by the following procedure. First, the chromium-containing layer is sputtered from its outermost surface, while the total content of the elements constituting the metallic chromium and the chromium compound and the Fe content are measured by the method described above. Then, the midpoint (1/2) between the position (depth) where the measured total content of the elements constituting the metallic chromium and the chromium compound and the Fe content are equal and the outermost surface of the chromium-containing layer is determined as the midpoint.
  • the above-mentioned XPS measurement can be performed using, for example, a scanning X-ray photoelectron spectrometer PHI X-tool manufactured by ULVAC-PHI, Inc.
  • the X-ray source is a monochrome AlK ⁇ ray
  • the voltage is 15 kV
  • the beam diameter is 100 ⁇ m ⁇
  • the take-off angle is 45°
  • the sputtering conditions are Ar ion with an acceleration voltage of 1 kV and a sputtering rate of 1.50 nm/min in terms of SiO2 .
  • the spatial structure of the components constituting the chromium-containing layer is not particularly limited, and may be, for example, separated as separate layers within the chromium-containing layer, or may be mixed throughout the chromium-containing layer. In other words, the spatial structure of the components constituting the chromium-containing layer may contain one or both of separate layers and mixed layers.
  • the chromium deposition amount of the chromium-containing layer is not particularly limited. However, if the chromium deposition amount of the chromium-containing layer is excessive, cohesive failure may occur in the chromium-containing layer when the surface-treated steel sheet is processed. Therefore, from the viewpoint of more stably ensuring the corrosion resistance of the BPA-free painted part, the chromium deposition amount of the chromium-containing layer is preferably 500.0 mg/m 2 or less per side, and more preferably 450.0 mg/m 2 or less.
  • the chromium deposition amount of the chromium-containing layer is preferably 40.0 mg/m 2 or more per side, and more preferably 50.0 mg/m 2 or more.
  • the "chromium deposition amount” refers to the total deposition amount of chromium present in various forms.
  • the amount of chromium adhesion can be measured by X-ray fluorescence analysis. More specifically, the amount of chromium adhesion is measured by the following procedure. First, an X-ray fluorescence device is used to measure the amount of Cr (total Cr amount) in the surface-treated steel sheet. Next, an X-ray fluorescence device is used to measure the amount of Cr (original sheet Cr amount) in the steel sheet before the chromium-containing layer is formed or in the steel sheet after the chromium-containing layer has been stripped. The value obtained by subtracting the original sheet Cr amount from the total Cr amount is the amount of chromium adhesion in the chromium-containing layer. To strip the chromium-containing layer, for example, a commercially available hydrochloric acid-based chromium plating stripper can be used.
  • Chromium oxide deposition amount Chromium oxide may be present in the chromium-containing layer.
  • the location of the chromium oxide is not particularly limited. The location of O can be confirmed by, for example, composition analysis using energy dispersive X-ray spectroscopy (EDS) or wavelength dispersive X-ray spectroscopy (WDS) attached to a scanning electron microscope (SEM) or a transmission electron microscope (TEM), or by three-dimensional composition analysis using a three-dimensional atom probe (3DAP).
  • EDS energy dispersive X-ray spectroscopy
  • WDS wavelength dispersive X-ray spectroscopy
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • 3DAP three-dimensional composition analysis using a three-dimensional atom probe
  • the amount of chromium oxide attached to the chromium-containing layer is not particularly limited. However, if the amount of chromium oxide attached to the chromium-containing layer is excessive, cohesive failure may occur starting from the Cr oxide in the chromium-containing layer when the surface-treated steel sheet is processed, and the corrosion resistance of the BPA-free painted part may deteriorate. Therefore, from the viewpoint of more stably ensuring the corrosion resistance of the BPA-free painted part, the amount of chromium oxide attached to the chromium-containing layer is preferably 40.0 mg/m 2 or less per side, more preferably 35.0 mg/m 2 or less. On the other hand, the chromium-containing layer may not contain chromium oxide at all. Therefore, the lower limit of the amount of chromium oxide attached to the chromium-containing layer is not particularly limited, and may be 0.0 mg/m 2 per side.
  • the amount of chromium oxide attached can be measured by X-ray fluorescence analysis. More specifically, the amount of chromium oxide attached is measured by the following procedure. First, the Cr amount (total Cr amount) of the surface-treated steel sheet is measured. Next, the surface-treated steel sheet is subjected to an alkali treatment by immersing it in 7.5N-NaOH at 90°C for 10 minutes to remove the chromium oxide. After the surface-treated steel sheet is thoroughly washed with water, the Cr amount (amount of Cr after alkali treatment) is measured again using an X-ray fluorescence device. The value obtained by subtracting the amount of Cr after alkali treatment from the total amount of Cr is determined as the amount of chromium oxide attached in the chromium-containing layer.
  • the chromium-containing layer may be amorphous or crystalline. That is, the chromium-containing layer may contain one or both of the amorphous and crystalline phases.
  • the chromium-containing layer manufactured by the method described below generally contains an amorphous phase, and may also contain a crystalline phase. The mechanism by which the chromium-containing layer is formed is not clear, but it is believed that the chromium-containing layer contains both the amorphous and crystalline phases as a result of partial crystallization occurring when the amorphous phase is formed.
  • the area ratio of the crystalline region is not particularly limited, but is preferably 30% or less when the chromium-containing layer is observed from the surface direction. On the other hand, since the crystalline region does not have to exist, the lower limit of the area ratio of the crystalline region may be 0%.
  • the crystalline region in the chromium-containing layer can be confirmed by removing the base steel sheet from the surface-treated steel sheet to prepare a chromium-containing layer single layer sample, and observing the chromium-containing layer single layer sample from the surface side with a TEM or STEM.
  • the method for preparing the chromium-containing layer single layer sample is not particularly limited, but for example, it can be prepared by irradiating an ion beam such as Ar from the base steel sheet side and ion milling the steel sheet.
  • the ion beam is irradiated with an acceleration voltage of 5 kV or less and an incidence angle in the range of 1 degree to 5 degrees relative to the base steel sheet, thereby ensuring a field of view of the chromium single layer region of several ⁇ m2 or more .
  • the bottom surface of the chromium-containing layer is also milled to some extent, and the film thickness of the chromium-containing layer may become thin, but this does not affect the measurement result of the area ratio of the crystalline region.
  • the area ratio of the crystalline regions in the chromium-containing layer can be measured by TEM. Specifically, a diffraction pattern of the chromium-containing layer is first obtained by selected area diffraction of the TEM. Next, dark-field images are obtained for all of the diffraction spots in the diffraction pattern, and the regions that appear with high brightness in the dark-field image are determined to be crystalline regions. The area of the obtained crystalline regions is calculated by image processing, and the area ratio of the crystalline regions is calculated by dividing the area of the chromium-containing layer within the selected area aperture. Image analysis software such as image-J can be used to calculate the area ratio.
  • the chromium-containing layer may contain C. There is no particular upper limit to the C content in the chromium-containing layer, but the atomic ratio to Cr is preferably 50% or less, and more preferably 45% or less.
  • the chromium-containing layer may not contain C, and therefore the lower limit of the atomic ratio of C to Cr contained in the chromium-containing layer is not particularly limited and may be 0%.
  • the C content in the chromium-containing layer can be measured by XPS. That is, the C content in the chromium-containing layer can be measured by sputtering from the outermost layer to a depth of 0.2 nm or more in terms of SiO2 , quantifying the integrated intensity of the narrow spectrum of Cr2p and C1s as an atomic ratio by the relative sensitivity coefficient method, and calculating the C atomic ratio/Cr atomic ratio.
  • XPS for example, a scanning X-ray photoelectron spectrometer PHI X-tool manufactured by ULVAC-PHI, Inc.
  • the X-ray source is a monochrome AlK ⁇ ray, the voltage is 15 kV, the beam diameter is 100 ⁇ m ⁇ , the take-off angle is 45°, and the sputtering conditions are Ar ion with an acceleration voltage of 1 kV and a sputtering rate of 1.50 nm/min in terms of SiO2 .
  • the location of C in the chromium-containing layer is not particularly limited.
  • the location of C can be confirmed, for example, by composition analysis using energy dispersive X-ray spectroscopy (EDS) or wavelength dispersive X-ray spectroscopy (WDS) attached to a scanning electron microscope (SEM) or transmission electron microscope (TEM), or by three-dimensional composition analysis using a three-dimensional atom probe (3DAP).
  • EDS energy dispersive X-ray spectroscopy
  • WDS wavelength dispersive X-ray spectroscopy
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • 3DAP three-dimensional composition analysis using a three-dimensional atom probe
  • the chromium-containing layer may contain Fe. There is no particular upper limit to the Fe content in the chromium-containing layer, but it is preferable that the atomic ratio to Cr is 100% or less.
  • the chromium-containing layer may not contain Fe, and therefore the lower limit of the atomic ratio to Cr is not particularly limited and may be 0%.
  • the Fe content in the chromium-containing layer can be measured by XPS, as with the C content.
  • the atomic ratio can be calculated using narrow spectra of Cr2p and Fe2p.
  • the chromium-containing layer may contain, in addition to Cr, O, Fe, and C, metal impurities such as K, Na, Mg, and Ca contained in the water, and Sn, Ni, Cu, and Zn contained in the aqueous solution, as well as S, N, Cl, Br, etc.
  • the presence of these elements may reduce the corrosion resistance of the BPA-free painted part. Therefore, the total of elements other than Cr, O, Fe, and C is preferably 3% or less in atomic ratio to Cr, and more preferably none (0%).
  • the content of the above elements is not particularly limited, but can be measured, for example, by XPS in the same way as the C content.
  • an oxygen-enriched region containing O at an atomic concentration of 10% or more exists in the vicinity of the interface between the steel sheet and the chromium-containing layer (hereinafter, the vicinity may be referred to as the interface vicinity region).
  • the interface vicinity region refers to a region in which the atomic ratio of Fe to Cr is in the range of 0.7 to 1.3. In this way, the presence of the oxygen-enriched region in the interface vicinity region can realize excellent corrosion resistance of the BPA-free paint-processed part.
  • the coverage of the oxygen-enriched region in the interface vicinity region is preferably 50% or more, more preferably 70% or more.
  • the upper limit of the coverage of the oxygen-enriched region in the interface vicinity region is not particularly limited and may be 100%.
  • the oxygen-enriched region refers only to the region existing in the interface vicinity region.
  • a typical chromium-containing layer formed from a hexavalent chromium bath or trivalent chromium bath is composed of metallic chromium and chromium oxide.
  • Surface-treated steel sheets with such a chromium-containing layer are generally processed into cans and the like after an organic resin coating is formed on the surface.
  • metallic chromium has poor workability, the chromium-containing layer cannot completely follow the deformation of the steel sheet that accompanies processing, and as a result, the organic resin coating present on the chromium-containing layer is damaged. This, in turn, results in a decrease in corrosion resistance after processing.
  • chromium oxide is applied as the top layer to ensure corrosion resistance after processing.
  • chromium oxide has excellent adhesion to epoxy-based paints, even if the metallic chromium is unable to follow the deformation of the base steel sheet, the chromium-containing layer and the epoxy-based paint adhere firmly, and the coating properties of the epoxy-based paint can be maintained even after can manufacturing.
  • the surface-treated steel sheet of the present invention provides an oxygen-enriched region in the region near the interface, thereby realizing excellent corrosion resistance in the BPA-free painted area. This is believed to be because the strain introduced into the chromium-containing layer during processing of the surface-treated steel sheet is dispersed, allowing the chromium-containing layer to follow the deformation of the steel sheet, and the oxygen-enriched region itself exhibits excellent corrosion resistance.
  • the present invention is based on a technical concept that is completely different from conventional ones, which is to improve the deformability of the chromium-containing layer itself and the corrosion resistance near the interface, rather than the adhesion to the paint.
  • the near-interface region and the oxygen-enriched region are determined as follows. First, five measurement regions are selected so as to include both the chromium-containing layer and the steel sheet, and five ion maps are obtained by performing three-dimensional composition analysis by 3DAP on the measurement regions. Next, the ion map is divided into voxels of 2 nm x 2 nm x 2 nm, and the composition of each voxel is calculated in atomic concentration. The region consisting of voxels in which the atomic ratio of Fe to Cr is in the range of 0.7 to 1.3 is determined as the near-interface region.
  • the region consisting of voxels in the near-interface region in which O is 10% or more in atomic concentration is determined as the oxygen-enriched region.
  • the atomic ratio of Fe to Cr and the atomic concentration of O are measured by three-dimensional composition analysis using a three-dimensional atom probe to determine the near-interface region and the oxygen-enriched region.
  • the position where the atomic ratio of Fe to Cr is 1.0 is considered to be the interface between the chromium-containing layer and the steel sheet. That is, the near-interface region includes the interface between the chromium-containing layer and the steel sheet.
  • the coverage is defined as follows. First, for each ion map, the number of voxels in the near-interface region is I, and the number of voxels in the oxygen-enriched region is O, and the percentage is calculated using the formula O/I x 100. The average value of the percentages for each ion map is then defined as the coverage of the oxygen-enriched region in the near-interface region. In this way, the coverage of the oxygen-enriched region is measured by three-dimensional composition analysis using a three-dimensional atom probe.
  • the oxygen-enriched region may contain C. There is no particular upper limit to the amount of C contained in the oxygen-enriched region, but it is preferably 20 atomic % or less.
  • the oxygen-enriched region may not contain C, and therefore there is no particular lower limit to the amount of C contained in the oxygen-enriched region, and it may be 0 atomic %.
  • the oxygen-enriched region may contain metals such as Si and Mn as oxides in addition to O, Fe, Cr, and C. However, if elements other than O, Fe, Cr, and C are present in large amounts, the corrosion resistance of the BPA-free painted part may decrease. From this perspective, it is preferable that the total content of O, Fe, Cr, and C in the oxygen-enriched region is 70 atomic % or more. From the same perspective, it is preferable that the oxygen-enriched region does not contain any oxides of Si and Mn (0%). The content of the above oxides can be measured, for example, by XPS.
  • the atomic concentration of each element in the oxygen-enriched region can be measured by three-dimensional composition analysis using 3DAP, in the same way as when determining the near-interface region and the oxygen-enriched region. More specifically, first, five measurement regions are selected to include both the chromium-containing layer and the steel plate, and five ion maps are obtained by performing three-dimensional composition analysis using 3DAP on the measurement regions. Next, the ion map is divided into voxels of 2 nm x 2 nm x 2 nm, and the composition of each voxel is calculated in terms of atomic concentration.
  • compositions of the voxels in the oxygen-enriched region are averaged to calculate the average composition for each ion map, i.e., the average composition for each measurement region.
  • the atomic concentration of each element in the oxygen-enriched region can be calculated by further averaging the average compositions for each measurement region.
  • the oxygen-enriched region may be amorphous or crystalline. That is, the oxygen-enriched region may contain one or both of the amorphous and crystalline phases. However, from the viewpoint of improving corrosion resistance, it is preferable that the oxygen-enriched region is amorphous. Whether the oxygen-enriched region is amorphous or not can be determined, for example, by preparing an observation sample including the oxygen-enriched region and observing the observation sample with a TEM or the like. That is, when a diffraction pattern of the oxygen-enriched region is obtained, if no diffraction spots appear in the diffraction pattern, the oxygen-enriched region is amorphous.
  • a surface-treated steel sheet having the above-mentioned properties can be produced by the method described below.
  • the method for producing a surface-treated steel sheet according to one embodiment of the present invention is a method for producing a surface-treated steel sheet having a chromium-containing layer on at least one side of the steel sheet, and includes a steel sheet surface conditioning process and a cathodic electrolytic treatment process. Each process will be described below.
  • a steel sheet surface conditioning step is performed in which the steel sheet is contacted with an aqueous solution containing sulfate ions and held for a predetermined time in a state in which a predetermined amount of the aqueous solution is present on the surface of the steel sheet. It is important to carry out the process.
  • Amount of aqueous solution more than 30.0 g/ m2 and not more than 60.0 g/ m2 Holding time: 0.10 to 20.0 seconds
  • the mechanism by which an oxygen-enriched region is formed in the region near the interface by the steel sheet surface conditioning process is not clear, but it is thought to be as follows.
  • an aqueous solution containing sulfate ions a dissolution reaction of Fe and a decomposition reaction of dissolved oxygen occur on the surface of the steel sheet, and the pH of the steel sheet surface rises.
  • the amount of the aqueous solution is within the above range, the thickness of the aqueous solution on the steel sheet becomes very thin, so that the amount of dissolved oxygen in the aqueous solution increases. As a result, the above reaction is further promoted.
  • the state in which the aqueous solution exists on the steel sheet is not particularly limited, but from the viewpoint of making the reaction uniform, it is preferable that the aqueous solution be in the form of a liquid film.
  • the Fe oxide accumulated in small amounts by the above method can form a chromium-containing layer on top of it even if it is not completely reduced in the subsequent cathodic electrolysis treatment process. As a result, it is presumed that an oxygen-enriched region is formed in the region near the interface.
  • the amount of the aqueous solution is preferably 32.0 g/m2 or more , and more preferably 35.0 g/m2 or more . From the same viewpoint, the amount of the aqueous solution is preferably 58.0 g/m2 or less , and more preferably 55.0 g/m2 or less .
  • the holding time is preferably 0.2 seconds or more, and more preferably 0.3 seconds or more. From the same viewpoint, the holding time is preferably 18.0 seconds or less, and more preferably 15.0 seconds or less.
  • the amount of the aqueous solution present on the surface of the steel sheet can be measured with a moisture meter using a filter type infrared absorption method. Specifically, the absorbance on the surface of the steel sheet is measured with a moisture meter using a filter type infrared absorption method, and the amount of the aqueous solution is calculated from the absorbance using a calibration curve that has been obtained in advance.
  • the calibration curve can be created by the following procedure. First, the steel sheet is placed on an electronic balance. The aqueous solution is dropped onto the steel sheet with a pipette to form a liquid film on the entire surface of the steel sheet.
  • the weight of the aqueous solution present on the steel sheet is calculated from the weight of the steel sheet before and after the aqueous solution is dropped.
  • the amount of the aqueous solution per unit area is calculated by dividing the weight of the aqueous solution obtained by dividing it by the area of the steel sheet.
  • the absorbance on the surface of the steel sheet is measured with a moisture meter using a filter type infrared absorption method. The above measurements are performed multiple times while changing the amount of aqueous solution, and a calibration curve that shows the correlation between the amount of aqueous solution and the absorbance is created. A linear approximation of the correlation between the amount of aqueous solution and the absorbance can be used as the calibration curve.
  • the method for adjusting the amount of aqueous solution present on the steel sheet surface is not particularly limited, and any method can be used.
  • a method of squeezing the liquid with a wringer roll or a method such as wiping can be used.
  • composition of the aqueous solution is not particularly limited, but it is preferably an aqueous sulfuric acid solution such as dilute sulfuric acid.
  • an aqueous sulfuric acid solution means an aqueous solution of sulfuric acid, and includes cases where components other than sulfuric acid are included.
  • the pickling solution can also be used as the aqueous solution in the steel sheet surface conditioning step.
  • Pickling solutions generally contain pickling inhibitors and pickling accelerators, but these components do not particularly hinder the formation of oxygen-enriched regions. Therefore, even if pickling inhibitors and pickling accelerators are added to the pickling solution, the pickling solution can be used as the aqueous solution in the steel sheet surface conditioning step.
  • the lower limit of the concentration of sulfate ions contained in the aqueous solution is not particularly limited, but is preferably 3 g/L or more, and more preferably 5 g/L or more.
  • the upper limit of the concentration of sulfate ions contained in the aqueous solution is not particularly limited, but is preferably 200 g/L or less, and more preferably 150 g/L or less.
  • the lower limit of the temperature of the aqueous solution is not particularly limited, but is preferably 10°C or higher, and more preferably 15°C or higher.
  • the upper limit of the temperature of the aqueous solution is not particularly limited, but is preferably 70°C or lower, and more preferably 60°C or lower.
  • the steel sheet is subjected to cathodic electrolysis in an electrolytic solution containing 0.05 mol/L or more of trivalent chromium ions.
  • the cathodic electrolysis can form a chromium-containing layer on the steel sheet.
  • Any compound that can supply trivalent chromium ions can be used as the trivalent chromium ion source.
  • at least one selected from the group consisting of chromium chloride, chromium sulfate, and chromium nitrate can be used as the trivalent chromium ion source.
  • the temperature of the electrolyte when performing the cathodic electrolysis is not particularly limited, but is preferably 40°C or higher in order to efficiently form a chromium-containing layer. For the same reason, it is preferable to set the temperature of the electrolyte to 70°C or lower. From the viewpoint of stably producing the above-mentioned surface-treated steel sheet, it is preferable to monitor the temperature of the electrolyte during the cathodic electrolysis process and maintain the temperature of the electrolyte in the temperature range of 40 to 70°C.
  • the pH of the electrolyte when performing the cathodic electrolysis is not particularly limited, but is preferably 4.0 or more, and more preferably 4.5 or more.
  • the pH is preferably 7.0 or less, and more preferably 6.5 or less. From the viewpoint of stably producing the above-mentioned surface-treated steel sheet, it is preferable to monitor the pH of the electrolyte during the cathodic electrolysis process and maintain it within the above pH range.
  • the current density in the cathodic electrolysis is not particularly limited, and may be appropriately adjusted so that a desired surface treatment layer is formed. However, if the current density is excessively high, the burden on the cathodic electrolysis treatment device becomes excessive. Therefore, the current density is preferably 200.0 A/dm 2 or less, and more preferably 100.0 A/dm 2 or less. In addition, although there is no particular limit to the lower limit of the current density, if the current density is excessively low, hexavalent Cr may be generated in the electrolytic solution, which may cause the stability of the bath to be lost. Therefore, the current density is preferably 5.0 A/dm 2 or more, and more preferably 10.0 A/dm 2 or more.
  • the number of times that the steel sheet is subjected to cathodic electrolysis is not particularly limited and can be any number of times.
  • cathodic electrolysis can be performed using an electrolytic treatment device having one or any number of passes, two or more.
  • the electrolysis time per pass is not particularly limited. However, if the electrolysis time per pass is too long, the conveying speed (line speed) of the steel sheet decreases, resulting in reduced productivity. Therefore, the electrolysis time per pass is preferably 5 seconds or less, and more preferably 3 seconds or less. There is no particular limit to the lower limit of the electrolysis time per pass, but if the electrolysis time is made too short, it becomes necessary to increase the line speed accordingly, making control difficult. Therefore, the electrolysis time per pass is preferably 0.005 seconds or more, and more preferably 0.01 seconds or more.
  • the amount of chromium deposited in the chromium-containing layer formed by cathodic electrolysis can be controlled by the total electric charge density, which is expressed as the product of the current density, the electrolysis time, and the number of passes.
  • the total electric charge density which is expressed as the product of the current density, the electrolysis time, and the number of passes.
  • the type of anode used when performing cathodic electrolysis is not particularly limited, and any anode can be used. It is preferable to use an insoluble anode as the anode. It is preferable to use at least one selected from the group consisting of an anode in which Ti is coated with one or both of a platinum group metal and an oxide of a platinum group metal, and a graphite anode as the insoluble anode. More specifically, examples of the insoluble anode include an anode in which the surface of Ti as a substrate is coated with platinum, iridium oxide, or ruthenium oxide.
  • the concentration of the electrolyte constantly changes due to the formation of a chromium-containing layer on the steel sheet, the introduction and removal of the liquid, the evaporation of water, etc.
  • the change in concentration of the electrolyte in the cathodic electrolytic treatment process varies depending on the configuration of the equipment and the manufacturing conditions, so from the perspective of more stable production of surface-treated steel sheets, it is preferable to monitor the concentration of the components contained in the electrolyte in the cathodic electrolytic treatment process and maintain it within the concentration range described below.
  • the water washing can be carried out by any method without any particular limitation.
  • a water washing tank can be provided downstream of the immersion tank used for the immersion treatment, and the steel sheet after immersion can be continuously immersed in water.
  • Water washing can also be carried out by spraying water onto the steel sheet after immersion.
  • the water used for the washing is not particularly limited, but it is preferable to use at least one of reverse osmosis water (RO water), ion-exchanged water, and distilled water.
  • the electrical conductivity of the water used for the washing is not particularly limited, but it is preferably 100 ⁇ S/m or less, more preferably 50 ⁇ S/m or less, and even more preferably 30 ⁇ S/m or less.
  • the temperature of the water used for the washing is not particularly limited and may be any temperature. However, an excessively high temperature places an excessive burden on the washing equipment, so the temperature of the water used for washing is preferably 95°C or less. On the other hand, the lower limit of the temperature of the water used for washing is not particularly limited, but it is preferably 0°C or higher. The temperature of the water used for the washing may be room temperature.
  • drying may be performed as desired.
  • the drying method There are no particular limitations on the drying method, and for example, a normal dryer or electric oven drying method can be used. From the viewpoint of suppressing deterioration of the surface treatment film, it is preferable that the temperature during the drying process be 100°C or less.
  • the lower limit is not particularly limited, but is usually around room temperature.
  • the steel sheet Before the steel sheet surface conditioning step, the steel sheet can be pretreated as desired.
  • the pretreatment preferably includes at least one of degreasing, pickling, and water washing.
  • degreasing rolling oil, rust-preventive oil, etc. adhering to the steel plate can be removed.
  • the degreasing can be carried out by any method without any particular restrictions. After degreasing, it is preferable to wash the steel plate with water to remove the degreasing treatment liquid adhering to the surface of the steel plate.
  • the natural oxide film present on the surface of the steel sheet can be removed, so that the surface can be effectively adjusted in the subsequent steel sheet surface adjustment process.
  • the pickling can be performed by any method without any particular limitation. After the pickling, it is preferable to rinse the steel sheet with water in order to remove the pickling solution adhering to the steel sheet surface. When an aqueous solution containing sulfate ions is used as the pickling solution, it is preferable to directly subject the steel sheet to the steel sheet surface adjustment process.
  • the trivalent chromium ion source can be any compound capable of supplying trivalent chromium ions.
  • at least one selected from the group consisting of chromium chloride, chromium sulfate, and chromium nitrate can be used as the trivalent chromium ion source.
  • the content of the trivalent chromium ion source in the aqueous solution must be 0.05 mol/L or more in terms of trivalent chromium ions, preferably 0.08 mol/L or more, and more preferably 0.10 mol/L or more.
  • the content of the trivalent chromium ion source is preferably 1.50 mol/L or less in terms of trivalent chromium ions, and more preferably 1.30 mol/L or less.
  • Atotech's BluCr (registered trademark) TFS A can be used as the trivalent chromium ion source.
  • the carboxylic acid compound is not particularly limited, and any carboxylic acid compound can be used.
  • the carboxylic acid compound may be at least one of a carboxylic acid and a carboxylate, and is preferably at least one of an aliphatic carboxylic acid and a salt of an aliphatic carboxylic acid.
  • the aliphatic carboxylic acid preferably has 1 to 10 carbon atoms, and more preferably has 1 to 5 carbon atoms.
  • the aliphatic carboxylate preferably has 1 to 10 carbon atoms, and more preferably has 1 to 5 carbon atoms.
  • the content of the carboxylic acid compound is not particularly limited, but is preferably 0.1 mol/L or more, and more preferably 0.15 mol/L or more.
  • the content of the carboxylic acid compound is preferably 5.5 mol/L or less, and more preferably 5.3 mol/L or less.
  • BluCr registered trademark
  • Water can be used as a solvent for preparing the aqueous solution. It is preferable to use at least one of ion-exchanged water and distilled water as the water.
  • the aqueous solution further contains at least one type of halide ion.
  • the content of the halide ion is not particularly limited, but is preferably 0.05 mol/L or more, and more preferably 0.10 mol/L or more.
  • the content of the halide ion is preferably 3.0 mol/L or less, and more preferably 2.5 mol/L or less.
  • Atotech's BluCr (registered trademark) TFS C1 and BluCr (registered trademark) TFS C2 can be used.
  • hexavalent chromium it is preferable not to add hexavalent chromium to the above-mentioned aqueous solution. It has been confirmed that in principle hexavalent chromium is not formed in the cathodic electrolytic treatment process, but even if a small amount of hexavalent chromium is formed at the anode, it is immediately reduced to trivalent chromium, so the concentration of hexavalent chromium in the electrolyte does not increase.
  • the aqueous solution described above is preferably free of intentional addition of metal ions other than trivalent chromium ions.
  • the metal ions are not limited, but may include Cu ions, Zn ions, Fe ions, Sn ions, Ni ions, etc., each of which is preferably 0 mg/L to 40 mg/L, more preferably 0 mg/L to 20 mg/L, and most preferably 0 mg/L to 10 mg/L.
  • Fe ions may dissolve in the above-mentioned electrolyte in the cathodic electrolytic treatment process and the immersion process and may be co-deposited in the film, but this does not affect the corrosion resistance of the BPA-free painted part.
  • the Fe ion concentration is within the above range when the bath is made, but it is also preferable to maintain the Fe ion concentration in the electrolyte within the above range in the cathodic electrolytic treatment process and the immersion process. If the Fe ions are controlled within the above range, the formation of the chromium-containing layer is not inhibited, and the required amount of the chromium-containing layer can be formed.
  • pH: 4.0-7.0 In preparing the electrolytic solution, it is preferable to adjust the pH of the aqueous solution after mixing to 4.0 to 7.0. It is more preferable to adjust the pH to 4.5 or more. It is more preferable to set it to 6.5 or less.
  • Any reagent can be used to adjust the pH.
  • the time for which the solution is held in the temperature range of 40 to 70° C. is not particularly limited.
  • the electrolyte obtained by the above procedure can be stably used in the cathodic electrolysis process for a long period of time.
  • the electrolyte produced by the above procedure can be stored at room temperature.
  • the uses of the surface-treated steel sheet of the present invention are not particularly limited, but it is particularly suitable as a surface-treated steel sheet for containers used in the manufacture of various containers such as food cans, beverage cans, pail cans, and 18-liter cans.
  • electrolyte solutions having compositions A to G shown in Table 1 were prepared under the conditions shown in Table 1. That is, each component shown in Table 1 was mixed with water to prepare an aqueous solution, and then the aqueous solution was adjusted to the pH and temperature shown in Table 1.
  • electrolyte solution G corresponds to the electrolyte solution used in the examples of Patent Document 4.
  • Ammonia water was used to increase the pH in all cases, and sulfuric acid was used for electrolyte solutions A, B, and G, hydrochloric acid was used for electrolyte solutions C and D, and nitric acid was used for electrolyte solutions E and F to decrease the pH.
  • Pretreatment of steel sheets A cold-rolled steel sheet was used as the steel sheet. More specifically, a can steel sheet (T4 base sheet) having a thickness of 0.17 mm was used. The steel sheet was subjected to electrolytic degreasing, water washing, and pickling in this order as pretreatment. For the pickling, an aqueous sulfuric acid solution having a sulfate ion concentration shown in Table 2 was used, and the steel sheet was immersed in the aqueous solution to perform pickling. The steel sheet after the pickling was subjected to the subsequent steel sheet surface conditioning step without being washed with water.
  • Step plate surface conditioning process Next, the steel sheet after the pickling was subjected to surface conditioning. Specifically, the pickling solution remaining on the surface of the steel sheet was squeezed with a wringer roll to remove the pickling solution. The amount of adhesion was adjusted to the amount shown as "amount of aqueous solution" in Table 2. Thereafter, the plate was held for the holding time shown in Table 2 while maintaining the amount of adhesion, and then washed with water to obtain the above pickling solution. The treatment solution was removed.
  • the amount of chromium deposited per side of the chromium-containing layer of the steel sheet and the amount of chromium oxide deposited per side of the steel sheet were measured using the method described above. Furthermore, for each of the obtained surface-treated steel sheets, the area in which the atomic ratio of Fe to Cr was in the range of 0.7 to 1.3 was determined as the vicinity of the interface between the steel sheet and the chromium-containing layer using the method described above. Then, the presence or absence of the oxygen-enriched area was determined by determining, using the method described above, an oxygen-enriched area in the vicinity where O was contained at an atomic concentration of 10% or more. Furthermore, the coverage rate of the oxygen-enriched area was measured using the method described above. The measurement results are shown in Table 3.
  • the chromium-containing layer obtained by cathodic electrolysis contained chromium compounds such as chromium oxide and chromium carbide in addition to metallic chromium.
  • the total content of the elements constituting the metallic chromium and chromium compounds in the chromium-containing layer was 90 mass% or more. It was also confirmed that the oxygen-enriched region did not contain oxides of Si and Mn. It was also confirmed that the oxygen-enriched region was composed of an amorphous material.
  • a BPA-free paint was applied to the surface of the surface-treated steel sheet to prepare a BPA-free painted steel sheet.
  • a polyester-based paint for the inner surface of a can (BPA-free paint) was used as the BPA-free paint.
  • the BPA-free paint was applied to the surface of the surface-treated steel sheet, and then the sheet was baked at 180°C for 10 minutes.
  • the coating weight was 60 mg/ dm2 .
  • the resulting BPA-free painted steel plate was then cut through to the base steel plate, and then an Erichsen tester was used to create a 4 mm high overhang centered on the intersection of the cross cut to prepare a test specimen.
  • test specimens were immersed in a Teflon (registered trademark) container containing test liquid and covered with a lid. In this state, they were subjected to a retort treatment at a temperature of 121°C for one hour. After that, the test specimens were removed from the container, washed with water to remove the test liquid, and then dried with a blower.
  • Teflon registered trademark
  • test pieces were tape-peeled twice, and the surface of the test piece was observed using a microscope or similar tool.
  • the areas of peeled paint and areas of discoloration such as rust were visually evaluated and scored on a 5-point scale, with 1 being the poorest and 5 being the best performance.
  • the same evaluation was performed on two samples per level, and the arithmetic mean of the scores was calculated and used as an index of the corrosion resistance of the BPA-free painted parts.
  • a score equal to or higher than that of conventional TFS can be evaluated as excellent in corrosion resistance of the BPA-free painted parts, but a score equal to or higher than that of conventional TFS and a score of 3.0 or higher is more preferable.
  • Citric acid Citric acid 19.2 g/L
  • L(+)-ascorbic acid 3.92 g/L

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Abstract

L'invention concerne une tôle d'acier traitée en surface qui peut être fabriquée sans utiliser de chrome hexavalent, et présente une excellente résistance à la corrosion dans une partie revêtue sans BPA Cette tôle d'acier traitée en surface comprend une tôle d'acier et une couche contenant du chrome disposée sur au moins une surface de la tôle d'acier : une région enrichie en oxygène contenant au moins 10 % d'O en termes de concentration atomique est présente à proximité d'une surface limite entre la tôle d'acier et la couche contenant du chrome ; et la proximité est une région dans laquelle le rapport atomique de Fe à Cr est compris entre 0,7 et 1,3.
PCT/JP2024/003164 2023-06-30 2024-01-31 Tôle d'acier traitée en surface et procédé de fabrication associé Ceased WO2025004426A1 (fr)

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JPH06108265A (ja) * 1992-09-29 1994-04-19 Nippon Steel Corp 塗装鋼板用下地塗布クロメート処理方法
JPH06340998A (ja) * 1993-06-01 1994-12-13 Nippon Parkerizing Co Ltd 陰極電解樹脂クロメート型金属表面処理方法
JPH10130891A (ja) * 1996-09-05 1998-05-19 Teikoku Piston Ring Co Ltd 複合Ｃｒめっき皮膜およびこれを有する摺動部材
JP2008050486A (ja) 2006-08-25 2008-03-06 Dainippon Ink & Chem Inc ３ｐ金属缶外面用ベースコート組成物及び該組成物の硬化塗膜層を有する３ｐ金属缶
JP2013144753A (ja) 2012-01-16 2013-07-25 Toyo Ink Sc Holdings Co Ltd 塗料組成物およびそれを用いた缶蓋
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JP2020172700A (ja) 2019-04-09 2020-10-22 ティッセンクルップ ラッセルシュタイン ゲー エム ベー ハー 三価クロム化合物を含む電解液を使用するクロムおよび酸化クロムのコーティングで被覆された金属ストリップの製造方法およびこの方法を実施するための電解システム
JP2020172701A (ja) 2019-04-09 2020-10-22 ティッセンクルップ ラッセルシュタイン ゲー エム ベー ハー ブラックプレート又はブリキの表面を不動態化するための方法及びその方法を実施するための電解システム
JP2021038429A (ja) * 2019-09-02 2021-03-11 オテック株式会社 複合化クロムめっき物品

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57131392A (en) * 1981-02-09 1982-08-14 Nippon Steel Corp Manufacture of electrolytically chromate-treated steel plate with high adhesion
JPH06108265A (ja) * 1992-09-29 1994-04-19 Nippon Steel Corp 塗装鋼板用下地塗布クロメート処理方法
JPH06340998A (ja) * 1993-06-01 1994-12-13 Nippon Parkerizing Co Ltd 陰極電解樹脂クロメート型金属表面処理方法
JPH10130891A (ja) * 1996-09-05 1998-05-19 Teikoku Piston Ring Co Ltd 複合Ｃｒめっき皮膜およびこれを有する摺動部材
JP2008050486A (ja) 2006-08-25 2008-03-06 Dainippon Ink & Chem Inc ３ｐ金属缶外面用ベースコート組成物及び該組成物の硬化塗膜層を有する３ｐ金属缶
JP2013144753A (ja) 2012-01-16 2013-07-25 Toyo Ink Sc Holdings Co Ltd 塗料組成物およびそれを用いた缶蓋
JP2016501985A (ja) 2012-11-21 2016-01-21 タタ、スティール、アイモイデン、ベスローテン、フェンノートシャップＴａｔａ Ｓｔｅｅｌ Ｉｊｍｕｉｄｅｎ Ｂｖ パッケージング用途のための鋼基材に適用されるクロム−酸化クロムコーティング及び前記コーティングを製造する方法
JP2016505708A (ja) 2012-11-21 2016-02-25 タタ、スティール、アイモイデン、ベスローテン、フェンノートシャップＴａｔａ Ｓｔｅｅｌ Ｉｊｍｕｉｄｅｎ Ｂｖ パッケージング用途のための鋼基材に適用されるクロム−酸化クロムコーティング及び前記コーティングを製造する方法
JP2020172700A (ja) 2019-04-09 2020-10-22 ティッセンクルップ ラッセルシュタイン ゲー エム ベー ハー 三価クロム化合物を含む電解液を使用するクロムおよび酸化クロムのコーティングで被覆された金属ストリップの製造方法およびこの方法を実施するための電解システム
JP2020172701A (ja) 2019-04-09 2020-10-22 ティッセンクルップ ラッセルシュタイン ゲー エム ベー ハー ブラックプレート又はブリキの表面を不動態化するための方法及びその方法を実施するための電解システム
JP2021038429A (ja) * 2019-09-02 2021-03-11 オテック株式会社 複合化クロムめっき物品

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