WO2013002356A1 - 表面処理鋼板、燃料パイプおよび電池缶 - Google Patents

表面処理鋼板、燃料パイプおよび電池缶 Download PDF

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WO2013002356A1
WO2013002356A1 PCT/JP2012/066641 JP2012066641W WO2013002356A1 WO 2013002356 A1 WO2013002356 A1 WO 2013002356A1 JP 2012066641 W JP2012066641 W JP 2012066641W WO 2013002356 A1 WO2013002356 A1 WO 2013002356A1
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Prior art keywords
treated steel
iron
steel sheet
alloy layer
nickel alloy
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PCT/JP2012/066641
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English (en)
French (fr)
Japanese (ja)
Inventor
友森　龍夫
興 吉岡
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東洋鋼鈑株式会社
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Priority to CN201280032782.6A priority Critical patent/CN103649362B/zh
Priority to JP2013522966A priority patent/JP6162601B2/ja
Priority to KR1020147002295A priority patent/KR20140053138A/ko
Priority to IN464CHN2014 priority patent/IN2014CN00464A/en
Publication of WO2013002356A1 publication Critical patent/WO2013002356A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L9/00—Rigid pipes
    • F16L9/16—Rigid pipes wound from sheets or strips, with or without reinforcement
    • F16L9/165—Rigid pipes wound from sheets or strips, with or without reinforcement of metal
    • 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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
    • C23C10/30—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes using a layer of powder or paste on the surface
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • 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
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L58/00—Protection of pipes or pipe fittings against corrosion or incrustation
    • F16L58/02—Protection of pipes or pipe fittings against corrosion or incrustation by means of internal or external coatings
    • F16L58/04—Coatings characterised by the materials used
    • F16L58/08—Coatings characterised by the materials used by metal
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L9/00—Rigid pipes
    • F16L9/02—Rigid pipes of metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/117—Inorganic material
    • H01M50/119—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/1245—Primary casings; Jackets or wrappings characterised by the material having a layered structure characterised by the external coating on the casing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
    • H01M50/145—Primary casings; Jackets or wrappings for protecting against damage caused by external factors for protecting against corrosion
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a surface-treated steel sheet, and a fuel pipe and a battery can obtained using the surface-treated steel sheet.
  • the Sn—Pb alloy has no corrosion resistance to water, and moreover, is more noble than Fe in terms of electric potential. Therefore, a pinhole is generated during hot dip plating, and this pinhole causes However, there is a problem that pitting corrosion occurs due to corrosive substances such as moisture inevitably contained in gasoline fuel.
  • Patent Document 1 a composite plating layer in which fluorine compound particles are dispersed in a nickel plating layer is formed on a steel plate surface by electroplating, and then heat treatment is performed at a temperature equal to or higher than the melting point of the fluorine compound particles.
  • the plated steel plate obtained by this is disclosed.
  • Patent Document 1 does not necessarily have a sufficient effect of suppressing the occurrence of pitting corrosion. Moreover, in the said patent document 1, since it uses a fluorine compound particle, it was not preferable from a viewpoint of environmental safety.
  • the present inventors have found that an iron-nickel alloy having an Fe / Ni value in the range of 0.3 to 2.0 by Auger electron spectroscopy analysis on the outermost surface. It has been found that the above object can be achieved by a surface-treated steel sheet formed with a layer, and the present invention has been completed.
  • a surface-treated steel sheet having an iron-nickel alloy layer formed on the outermost surface, the Fe / Ni value on the surface of the iron-nickel alloy layer is 0.
  • a surface-treated steel sheet characterized by being in the range of 3 to 2.0 is provided.
  • a fuel pipe formed by forming any one of the above surface-treated steel sheets.
  • a battery can formed by molding any one of the above surface-treated steel sheets.
  • pitting corrosion is generated by forming, on the outermost surface, an iron-nickel alloy layer having an Fe / Ni value in the range of 0.3 to 2.0 by Auger electron spectroscopy analysis on the outermost surface.
  • an iron-nickel alloy layer having an Fe / Ni value in the range of 0.3 to 2.0 by Auger electron spectroscopy analysis on the outermost surface.
  • FIG. 1 is a diagram for explaining a corrosion pattern of a metal plate.
  • the surface-treated steel sheet of the present invention is a surface-treated steel sheet in which an iron-nickel alloy layer is formed on the outermost surface, and the Fe / Ni value by the Auger electron spectroscopic analysis on the surface of the iron-nickel alloy layer is 0. It is characterized by being in the range of 3 to 2.0.
  • the steel sheet used as the substrate of the surface-treated steel sheet of the present invention is not particularly limited as long as it has excellent workability.
  • a low carbon aluminum killed steel carbon content 0.01 to 0.15% by weight
  • An ultra-low carbon steel having a carbon content of 0.003% by weight or less, or a non-aging ultra-low carbon steel obtained by further adding Ti or Nb to an ultra-low carbon steel can be used.
  • these steel hot-rolled plates are pickled to remove the surface scale (oxide film), then cold-rolled, then electrolytically washed with rolling oil, and then annealed and temper-rolled.
  • a thing is used as a substrate.
  • the annealing may be either continuous annealing or box annealing, and is not particularly limited.
  • the surface-treated steel sheet of the present invention has an iron-nickel alloy layer formed on the outermost surface.
  • the iron-nickel alloy layer has an Fe / Ni value (Fe / Ni molar ratio) in the range of 0.3 to 2.0, preferably 0.3 to 1.5, on the surface by Auger electron spectroscopy. It is a range.
  • the corrosion resistance can be improved.
  • nickel-plated steel sheets have been used in fields where corrosion resistance is required, such as pipes and battery cans for various fuels such as fuel oil for automobiles, because they have high corrosion resistance.
  • the nickel plating layer is formed by electroplating, there is a problem that pinholes are generated.
  • the present inventors formed an iron-nickel alloy layer in which the Fe / Ni value by Auger electron spectroscopic analysis was controlled in the above range on the surface of the steel sheet, thereby providing excellent corrosion resistance with the nickel plating layer.
  • the present invention has been completed by finding out that the occurrence of pitting corrosion can be effectively suppressed while securing the above.
  • the present inventors have found that the generation of pitting corrosion can be effectively suppressed while ensuring excellent corrosion resistance of the nickel plating layer by intentionally dispersing iron in the nickel layer having high corrosion resistance. is there.
  • FIG. 1A is a view showing a metal plate before corrosion occurs
  • FIG. 1B is a view showing a metal plate where pitting corrosion has occurred
  • FIG. 1C is a metal where overall corrosion has occurred. It is a figure which shows a board.
  • FIG. 1C shows an example in which the thickness of the metal plate is reduced from t 0 to t 1 .
  • the Fe / Ni value is too low, pitting corrosion occurs as shown in FIG. 1 (B).
  • FIG. 1 (B) shows that the Fe / Ni value is too high, FIG. The progress rate of the overall corrosion shown in the figure is increased, and as a result, the entire thickness is reduced.
  • the Fe / Ni value by Auger electron spectroscopy can be measured by the following method, for example. That is, first, the surface of the iron-nickel alloy layer is measured using a scanning Auger electron spectrometer (AES), and the atomic% of Ni and Fe on the surface of the iron-nickel alloy layer is calculated. Then, the surface of the iron-nickel alloy layer was measured with a scanning Auger electron spectrometer at five locations, and the obtained results were averaged to obtain an Fe / Ni value (Fe atomic% / Ni Atomic%) can be calculated.
  • AES scanning Auger electron spectrometer
  • a peak at 820 to 850 eV is a Ni peak
  • a peak at 570 to 600 eV is a Fe peak.
  • Fe is taken as 100 atomic%, and atomic% of Ni and Fe is measured.
  • the iron-nickel alloy layer has an Fe / Ni value by the Auger electron spectroscopic analysis in the above range, and the immersion potential in the aqueous sodium chloride solution
  • the immersion potential in the aqueous sodium chloride solution is preferably in the range of +0.05 to +0.25 V, more preferably in the range of +0.07 to +0.22 V. That is, it is preferable that the difference from the immersion potential of iron alone in the aqueous sodium chloride solution is in the above range.
  • the effect of suppressing pitting corrosion can be further improved by setting the immersion potential in the aqueous sodium chloride solution within the above range. If the immersion potential of the iron-nickel alloy layer is too low (if the difference from the immersion potential of iron alone is too small), the corrosion resistance of the iron-nickel alloy layer will decrease and the corrosion rate on the entire surface of the alloy layer will increase. End up. On the other hand, if the immersion potential is too noble (if the difference from the immersion potential of the iron simple substance is too large), the effect of suppressing the occurrence of pitting corrosion is reduced.
  • the immersion potential of the iron-nickel alloy layer in the sodium chloride aqueous solution is, for example, the natural potential 15 minutes after the iron-nickel alloy layer is immersed in a 5 wt% sodium chloride aqueous solution.
  • the potential can be measured and used as the immersion potential.
  • the time for immersing the iron-nickel alloy layer in the sodium chloride aqueous solution can be set based on the time required for the value of the natural potential to stabilize after the immersion, for example, 15 minutes as described above. Can be set.
  • the electrolyte solution was a 5% by weight aqueous sodium chloride solution, and the measurement was performed under the conditions of a reference electrode: Ag / AgCl, a counter electrode: Pt, and a measurement temperature of 35 ° C. It can be measured by measuring the natural potential with respect to Ag / AgCl and determining the difference between the obtained natural potential and the natural potential with respect to Ag / AgCl of the simple substance of Fe.
  • the difference in potential of the iron-nickel alloy layer from the immersion potential of the iron-nickel alloy layer in the sodium chloride aqueous solution relative to the immersion potential of the simple iron is “the immersion potential of the iron-nickel alloy layer” — This is a potential difference calculated by “immersion potential of iron alone”.
  • the method for forming the iron-nickel alloy layer is not particularly limited, and examples thereof include the following methods. That is, a method of forming an iron-nickel alloy layer by forming a nickel plating layer on the surface of a steel sheet using a nickel plating bath and then thermally diffusing it with a heat treatment is exemplified.
  • the method for forming the iron-nickel alloy layer is not particularly limited to such a method.
  • a plating bath usually used in nickel plating that is, a Watt bath, a sulfamic acid bath, a citric acid bath, a borofluoride bath, a chloride bath, etc.
  • a nickel plating layer having a thickness of 0.3 to 5 ⁇ m, preferably 0.3 to 2 ⁇ m is formed.
  • the nickel plating layer uses a bath composition of nickel sulfate 200 to 350 g / L, nickel chloride 20 to 50 g / L, boric acid 20 to 50 g / L as a watt bath, pH 3 to 4.8, bath temperature 40 It can be formed at a temperature of ⁇ 70 ° C.
  • the thickness of the nickel plating layer is too thin, the alloy layer formed in the subsequent process becomes thin, so that the corrosion resistance on the entire surface of the alloy layer may be reduced. On the other hand, if the thickness is too thick, sufficient iron is contained in the heat treatment in the subsequent process. There is a possibility that an alloy cannot be formed without diffusion, and this leads to an increase in cost.
  • the steel plate on which the nickel plating layer is formed is thermally diffused by heat treatment to form an iron-nickel alloy layer (iron-nickel diffusion layer).
  • the heat treatment may be performed by either continuous annealing or box annealing, and the heat treatment conditions may be appropriately selected according to the thickness of the nickel plating layer.
  • the heat treatment is performed by the following conditions, the following conditions are preferable.
  • Heat treatment temperature 400-800 ° C
  • Heat treatment time 30 minutes to 16 hours
  • Heat treatment atmosphere non-oxidizing atmosphere or reducing protective gas atmosphere
  • the following conditions are preferable.
  • Heat treatment temperature 600-900 ° C
  • Heat treatment time 3 seconds to 120 seconds
  • Heat treatment atmosphere non-oxidizing atmosphere or reducing protective gas atmosphere
  • the heat treatment temperature is too low or the heat treatment time is too short, the thermal diffusion in the iron-nickel alloy layer will be insufficient, and the Fe / Ni value on the iron-nickel alloy layer surface by Auger electron spectroscopy will be low, As a result, the effect of suppressing the occurrence of pitting corrosion cannot be obtained.
  • the heat treatment temperature is too high or the heat treatment time is too long, the Fe / Ni value on the surface of the iron-nickel alloy layer by Auger electron spectroscopy becomes too high, and the corrosion resistance of the iron-nickel alloy layer decreases. The corrosion rate on the entire surface of the alloy layer is increased.
  • the surface-treated steel sheet of the present invention can be obtained by forming the predetermined iron-nickel alloy layer described above on the steel sheet.
  • the surface-treated steel sheet of the present invention has pores when exposed to corrosive liquid contents or steam, for example, when exposed to various fuels such as automotive fuel oil, or when exposed to battery electrolyte. The occurrence of food is effectively suppressed and the corrosion resistance is excellent. Therefore, the surface-treated steel sheet of the present invention can be suitably used for applications that are used in a state exposed to liquid contents such as various fuels. Specifically, it can be suitably used for various applications such as a fuel pipe, a fuel tank, and a battery can.
  • the surface-treated steel sheet of the present invention can exhibit excellent corrosion resistance as compared with materials conventionally used for beverage cans and food cans, and thus beverage cans. It can also be suitably used for food and can applications.
  • the iron-nickel alloy layer constituting the surface-treated steel sheet of the present invention is a sufficiently alloyed iron and nickel, even when used in these beverage cans and food cans, Elution can be suppressed appropriately.
  • the fuel pipe of the present invention is obtained by forming the surface-treated steel sheet of the present invention described above. Specifically, in the fuel pipe of the present invention, the surface-treated steel sheet of the present invention described above is modified with a leveler and slit to a predetermined outer diameter with a slitter, and then the iron-nickel alloy layer comes to the inner surface side.
  • a fuel pipe can be obtained by pipe-forming with a molding machine and seam welding the end faces in the longitudinal direction by high-frequency induction welding. Since the fuel pipe of the present invention obtained in this way uses the surface-treated steel sheet of the present invention described above, pitting corrosion occurs when exposed to various fuels such as fuel oil for automobiles. It is effectively suppressed and has excellent corrosion resistance.
  • the fuel pipe of the present invention can be suitably used for various applications such as an oil supply pipe that introduces fuel into a tank, a pipe that introduces fuel from a tank into an engine, and a pipe that ventilates.
  • examples of the fuel include various fuels for automobiles such as gasoline, light oil, bioethanol, or biodiesel fuel.
  • the battery can of the present invention is obtained using the above-described surface-treated steel sheet of the present invention.
  • the battery can of the present invention is formed by forming the above-described surface-treated steel sheet of the present invention by drawing, ironing, DI or DTR so that the iron-nickel alloy layer is on the battery can inner surface side. Obtainable. Since the battery can of the present invention thus obtained is made using the above-described surface-treated steel sheet of the present invention, the occurrence of pitting corrosion is effectively suppressed and the corrosion resistance is excellent.
  • the above-described surface-treated steel sheet of the present invention is effective in generating pitting corrosion not only when exposed to various fuels such as fuel oil for automobiles but also when used in contact with a strong alkaline electrolyte. And can achieve excellent corrosion resistance. Therefore, the battery can of the present invention can be suitably used as a battery container for a battery using a strong alkaline electrolyte such as an alkaline battery or a nickel metal hydride battery.
  • ⁇ Fe / Ni value> The outermost layer of the iron-nickel alloy layer of the surface-treated steel sheet was etched by about 10 nm, and the surface-treated steel sheet after etching was subjected to Ni and Fe atoms at five locations using a scanning Auger electron spectrometer (AES). % Of Fe / Ni was determined by Auger electron spectroscopic analysis.
  • the surface-treated steel sheet masked leaving a region of ⁇ 5 mm was immersed in a 5% by weight sodium chloride aqueous solution, and the conditions of the reference electrode: Ag / AgCl, the counter electrode: Pt, and the measurement temperature of 35 ° C.
  • the immersion potential in the sodium chloride aqueous solution of the iron-nickel alloy layer can be measured. I did it.
  • ⁇ Pitting corrosion> The surface-treated steel sheet masked leaving a 20 ⁇ 20 mm area is immersed in a 5% by weight aqueous sodium chloride solution, and the potential is forced under the conditions of a reference electrode: Ag / AgCl, a counter electrode: Pt, and a measurement temperature of 35 ° C.
  • the anodic polarization was carried out gradually, and the corrosion was promoted by maintaining the potential at the point where corrosion of the surface-treated steel sheet started for 30 minutes. And as a result of accelerating corrosion, whether or not pitting corrosion occurred in the surface-treated steel sheet in a 20 ⁇ 20 mm region was visually observed.
  • Example 1 As a substrate, a steel sheet obtained by annealing a cold rolled sheet (thickness: 0.25 mm) of low carbon aluminum killed steel having the chemical composition shown below was prepared.
  • the steel plate on which the nickel plating layer is formed is subjected to heat treatment under the conditions of a non-oxidizing atmosphere (vacuum annealing) at a temperature of 650 ° C. for 2 hours by box annealing, and a thermal diffusion treatment is performed on the nickel plating layer, An iron-nickel alloy layer was formed to obtain a surface-treated steel sheet.
  • the surface-treated steel sheet thus obtained was evaluated according to the above method for Fe / Ni value by Auger electron spectroscopic analysis, immersion potential in sodium chloride aqueous solution, and occurrence of pitting corrosion. The results are shown in Table 1.
  • Example 2 A surface-treated steel sheet was obtained and evaluated in the same manner as in Example 1 except that the heat treatment time was changed to 4 hours. The results are shown in Table 1.
  • Example 3 A surface-treated steel sheet was obtained and evaluated in the same manner as in Example 2 except that the thickness of the nickel plating layer was set to 1 ⁇ m. The results are shown in Table 1.
  • Example 4 A surface-treated steel sheet was obtained and evaluated in the same manner as in Example 1 except that the heat treatment time was changed to 8 hours. The results are shown in Table 1.
  • Example 5 A surface-treated steel sheet was obtained and evaluated in the same manner as in Example 3 except that the heat treatment time was changed to 8 hours. The results are shown in Table 1.
  • Example 6 A surface-treated steel sheet was obtained and evaluated in the same manner as in Example 1 except that the thickness of the nickel plating layer was 2 ⁇ m and the heat treatment time was changed to 12 hours. The results are shown in Table 1.
  • Example 7 A surface-treated steel sheet was obtained and evaluated in the same manner as in Example 1 except that the heat treatment was changed to continuous annealing in a non-oxidizing atmosphere (vacuum annealing) at a temperature of 800 ° C. for 1 minute. The results are shown in Table 1.
  • Example 8 A surface-treated steel sheet was obtained and evaluated in the same manner as in Example 7 except that the heat treatment temperature was changed to 900 ° C. The results are shown in Table 1.
  • Comparative Example 1 A surface-treated steel sheet was obtained and evaluated in the same manner as in Example 1 except that no heat treatment was performed. The results are shown in Table 1.
  • Comparative Examples 2 to 4 A surface-treated steel sheet was obtained in the same manner as in Comparative Example 1 except that the thickness of the nickel plating layer was 1 ⁇ m (Comparative Example 2), 2 ⁇ m (Comparative Example 3), and 3 ⁇ m (Comparative Example 4), respectively. Was evaluated. The results are shown in Table 1.
  • Comparative Example 5 A surface-treated steel sheet was obtained and evaluated in the same manner as in Example 1 except that the thickness of the nickel plating layer was 1 ⁇ m. The results are shown in Table 1.
  • Comparative Example 6 >> A surface-treated steel sheet was obtained and evaluated in the same manner as in Example 1 except that the thickness of the nickel plating layer was 3 ⁇ m. The results are shown in Table 1.
  • Comparative Examples 7 and 8 >> A surface-treated steel sheet was obtained and evaluated in the same manner as in Comparative Example 6, except that the heat treatment time was 4 hours (Comparative Example 7) and 8 hours (Comparative Example 8), respectively. The results are shown in Table 1.
  • Comparative Example 9 A surface-treated steel sheet was obtained and evaluated in the same manner as in Example 7 except that the heat treatment temperature was changed to 720 ° C. The results are shown in Table 1.
  • Comparative Example 10 A surface-treated steel sheet was obtained and evaluated in the same manner as in Example 3 except that the heat treatment was changed to continuous annealing at a temperature of 720 ° C. for 1 minute and a non-oxidizing atmosphere (vacuum annealing). The results are shown in Table 1.
  • Comparative Example 11 A surface-treated steel sheet was obtained and evaluated in the same manner as in Comparative Example 10 except that the heat treatment temperature was changed to 800 ° C. The results are shown in Table 1.
  • Comparative Example 12 A surface-treated steel sheet was obtained and evaluated in the same manner as in Comparative Example 10, except that the heat treatment temperature was changed to 900 ° C. The results are shown in Table 1.
  • Examples 1 to 8 where the Fe / Ni value in the range of 0.3 to 2.0 by Auger electron spectroscopic analysis on the surface of the iron-nickel alloy layer, the occurrence of pitting corrosion is suppressed.
  • the immersion potential for iron alone in the aqueous sodium chloride solution was within the range of +0.05 to +0.25 V.
  • the Fe / Ni value by the Auger electron spectroscopic analysis on the surface of the iron-nickel alloy layer was less than 0.3
  • pitting corrosion occurs, and therefore, when used in a state exposed to corrosive liquid contents, such as for fuel pipes and battery cans, the contents are caused through pitting corrosion. May leak to the outside.

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  • Electrochemistry (AREA)
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  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
PCT/JP2012/066641 2011-06-30 2012-06-29 表面処理鋼板、燃料パイプおよび電池缶 WO2013002356A1 (ja)

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WO2022176553A1 (ja) * 2021-02-19 2022-08-25 東洋鋼鈑株式会社 電池容器用鋼箔及びそれにより製造されるパウチ型電池容器

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WO2019021909A1 (ja) * 2017-07-28 2019-01-31 Ｊｆｅスチール株式会社 電池外筒缶用鋼板、電池外筒缶および電池
CN110945155B (zh) * 2017-07-28 2022-06-07 杰富意钢铁株式会社 电池外筒罐用钢板、电池外筒罐及电池
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JP6400140B2 (ja) 2018-10-03
JP6162601B2 (ja) 2017-07-12
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