WO2019198819A1 - Ni拡散めっき鋼板及びNi拡散めっき鋼板の製造方法 - Google Patents
Ni拡散めっき鋼板及びNi拡散めっき鋼板の製造方法 Download PDFInfo
- Publication number
- WO2019198819A1 WO2019198819A1 PCT/JP2019/015978 JP2019015978W WO2019198819A1 WO 2019198819 A1 WO2019198819 A1 WO 2019198819A1 JP 2019015978 W JP2019015978 W JP 2019015978W WO 2019198819 A1 WO2019198819 A1 WO 2019198819A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- steel sheet
- diffusion
- plating layer
- less
- plating
- Prior art date
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 204
- 239000010959 steel Substances 0.000 title claims abstract description 204
- 238000009792 diffusion process Methods 0.000 title claims abstract description 143
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 238000007747 plating Methods 0.000 claims abstract description 194
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 82
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 70
- 239000000956 alloy Substances 0.000 claims abstract description 70
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 14
- 238000000137 annealing Methods 0.000 claims description 49
- 238000010438 heat treatment Methods 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 21
- 238000002791 soaking Methods 0.000 claims description 18
- 238000009713 electroplating Methods 0.000 claims description 17
- 150000002500 ions Chemical class 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 2
- 239000012611 container material Substances 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 184
- 239000010410 layer Substances 0.000 description 136
- 239000002585 base Substances 0.000 description 65
- 238000000034 method Methods 0.000 description 42
- 239000000463 material Substances 0.000 description 40
- 239000013078 crystal Substances 0.000 description 31
- 238000005097 cold rolling Methods 0.000 description 26
- 238000005096 rolling process Methods 0.000 description 26
- 238000005275 alloying Methods 0.000 description 25
- 239000010960 cold rolled steel Substances 0.000 description 18
- 229910000655 Killed steel Inorganic materials 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 239000011572 manganese Substances 0.000 description 14
- 238000005098 hot rolling Methods 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 12
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 11
- 238000005259 measurement Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 230000007547 defect Effects 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- 239000002344 surface layer Substances 0.000 description 7
- 229910052796 boron Inorganic materials 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- 238000003483 aging Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 239000006104 solid solution Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000000992 sputter etching Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000009924 canning Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000012733 comparative method Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- -1 nickel metal hydride Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910001562 pearlite Inorganic materials 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910001295 No alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000001336 glow discharge atomic emission spectroscopy Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000002436 steel type Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Definitions
- the present invention relates to a Ni diffusion plated steel sheet and a method for producing a Ni diffusion plated steel sheet.
- Ni-plated steel sheet is used as a material for containers (battery cans) of various batteries such as alkaline manganese batteries, lithium ion batteries, nickel metal hydride batteries, etc., because Ni has excellent chemical stability.
- Ni plating methods for battery cans include barrel plating after can making and plating on steel strip before can making, but in terms of manufacturing cost and uniformity of plating, steel before can making The method of plating the strip is advantageous.
- a Ni-plated steel sheet that has been Ni-plated before canning may cause cracks in the Ni-plated layer due to processing during canning.
- Ni plating is a barrier-type anticorrosive film, and does not have sacrificial anticorrosive properties like a Zn plating film. Therefore, if pinholes or cracks exist in the Ni plating layer, the corrosion resistance may be lowered.
- the Ni plating layer having a thickness of 1 to 5 ⁇ m is applied to the cold-rolled steel sheet, and then a part or all of the Ni plating layer is dealt with.
- a Fe—Ni diffusion alloy layer is formed at the interface between the Ni plating and the steel plate, and the adhesion of the plating layer is improved (hereinafter, by heat-treating the Ni-plated steel plate, At least a steel sheet in which an Fe—Ni diffusion alloy layer is formed at the interface between the Ni plating and the steel sheet is referred to as “Ni diffusion plated steel sheet”).
- the Ni phase recrystallizes due to the heating history.
- the Ni plating layer is soft, it is difficult to crack during processing, and exposure of the base steel sheet after processing can be suppressed.
- the recrystallized soft Ni plating layer tends to seize on the mold at the time of pressing, and the reduction in productivity becomes a problem.
- Patent Document 2 has an Fe—Ni diffusion layer formed by performing a thermal diffusion treatment after forming a Ni plating layer on at least the inner surface of the battery container of the steel plate, and Fe—Ni
- the ratio of Ni and Fe in the outermost layer of the diffusion layer is 7.5 or less in terms of Ni / Fe molar ratio, and the thickness of the Fe—Ni diffusion layer is 0.6 ⁇ m or more.
- a surface-treated steel sheet for a battery container for forming a battery container for a battery using an electrolytic solution is disclosed.
- Patent Document 2 describes that in the case of continuous annealing, it is preferable to set the heat treatment temperature to 700 to 800 ° C. and the heat treatment time to 10 to 300 seconds as conditions for the thermal diffusion treatment.
- a Ni plating layer having a thickness of 1 ⁇ m can be alloyed by heat treatment so that the surface layer of the plating layer has a predetermined Fe concentration.
- the composition of the outermost layer of the plating layer refers to the Auger electron spectroscopy after removing the contaminating layer or oxide layer that may be present on the surface of the plating layer by argon ion etching. This refers to the composition of the surface observed by the method (Auger Electron Spectroscopy: AES).
- Main characteristics required for steel plates for cans are (1) press formability (mould be formed without defects such as cracks during processing), (2) resistance Roughness (small surface roughness after press working), (3) Earring resistance (small material anisotropy and small earing after deep drawing), (4) Non-aging (during drawing) Stretcher strain does not occur).
- a base steel plate for can steel plates (particularly battery can steel plates), mainly Al-killed steel plates or IF steel steel plates (IF: Interstitial Free, ultra-low carbon Ti-added steel, ultra-low carbon Nb-added steel, Extremely low carbon Ti—Nb-added steel, etc.) are used.
- Al-killed steel sheet when compared with IF-based steel sheets, but to ensure the average plastic strain ratio r m of the high level is the somewhat difficult, refinement of ferrite crystal grains can be easily compared to the IF system steel Continuous annealing for recrystallization is also possible at a relatively low temperature.
- the recrystallization temperature is lower than that of the IF steel system (thus, In the case of using an Al-killed steel sheet having a low appropriate continuous annealing temperature, the interdiffusion of Fe-Ni cannot be sufficiently caused during the continuous annealing process.
- the Al-killed steel sheet is preferable from the viewpoint of rough skin resistance because it is easy to make the ferrite crystal grains finer.
- the average plastic strain ratio r m of the above refers to a value defined by the following formula (I).
- r m (r 0 + 2 ⁇ r 45 + r 90 ) / 4 (I)
- r 0 the rolling direction r value
- r 90 the rolling direction orthogonal r value
- r 45 a 45 ° direction r value
- r value is a plastic strain ratio (Lankford value) .
- the corrosion resistance becomes insufficient.
- the plating thickness is more than 1 ⁇ m, it is unavoidable to select a condition for the thermal diffusion treatment to be on the high temperature side or the long time side, and the base crystal grains are coarse as described above. Invite The coarsening of the base material crystal grains causes a problem of deterioration of rough skin resistance, particularly as a material for cans.
- the present invention has been made in view of the above problems, and the object of the present invention is to improve the corrosion resistance and the mold slidability while maintaining the characteristics of the Al-killed steel base material. It is providing the manufacturing method of Ni diffusion plating steel plate and Ni diffusion plating steel plate.
- the present inventors have found that when the plating bath composition satisfies a specific condition, Fe easily diffuses in the Ni plating layer, and this knowledge is obtained from a specific Al-killed steel system. As a result, the present invention has been completed.
- the present inventors when applying Ni electroplating on a steel sheet, the present inventors employ a Ni electroplating bath containing a chloride ion concentration of 35 g / L or more, thereby enabling Fe—Ni alloying in thermal diffusion treatment. It was found that this was remarkably accelerated as compared with the case of using a Watts bath or the like.
- the present inventors succeeded in obtaining a desired Ni diffusion plated steel sheet by applying Ni electroplating based on such knowledge using a specific Al-killed steel steel sheet as a base material.
- the gist of the present invention completed based on such findings is as follows.
- a Ni diffusion plated steel sheet includes a base steel sheet and an Fe—Ni diffusion alloy plating layer located on at least one surface of the base steel sheet, and the Fe—Ni diffusion alloy.
- the Ni adhesion amount of the plating layer is 9.0 to 20 g / m 2
- the Fe concentration Cs of the outermost layer of the Fe—Ni diffusion alloy plating layer is 10 to 55% by mass
- Composition is mass%, C: 0.005 to 0.250%, Si: 0.1% or less, Mn: 0.05 to 0.90%, P: 0.025% or less, S: 0.025 % Or less, sol.
- the Fe concentration Cs of the outermost layer of the Fe—Ni diffusion alloy plating layer may be 15 to 40% by mass.
- the Ni diffusion plated steel sheet according to (1) or (2) is used as a material for a container, and the Fe-Ni diffusion alloy plating is applied to the base steel sheet on the side that becomes the outer surface of the container by press forming. A layer may be provided.
- a method for producing a Ni diffusion plated steel sheet has a chloride ion concentration of 35.0 g on at least one surface of a base steel sheet having the chemical composition described in (1).
- Ni forming a Ni plating layer having an adhesion amount of 9.0 to 20 g / m 2 by electroplating using a Ni plating bath having a Ni ion concentration of 40.0 g / L or more.
- heat treatment is performed at a temperature range of 670 to 760 ° C. for a soaking time of 5 to 180 seconds, so that the Fe concentration Cs of the outermost layer of the Ni plating layer is 10 to 55% by mass.
- An annealing / alloying process is performed at a temperature range of 670 to 760 ° C. for a soaking time of 5 to 180 seconds.
- Ni diffusion plated steel sheet As described above, according to the present invention, it is possible to obtain a Ni diffusion plated steel sheet and a method for producing a Ni diffusion plated steel sheet that are excellent in corrosion resistance and mold slidability while maintaining the characteristics of an Al-killed steel base material. Is possible.
- FIGS. 1A and 1B are explanatory views schematically showing an example of the structure of a Ni diffusion plated steel sheet according to the present embodiment.
- the Ni diffusion plated steel sheet 1 includes at least a base steel sheet 11 and an Fe—Ni diffusion alloy plating layer 13 positioned on the base steel sheet 11.
- the Fe—Ni diffusion alloy plating layer 13 according to the present embodiment may be provided on one surface of the base steel plate 11 as schematically shown in FIG. 1A, or schematically shown in FIG. 1B.
- the base steel plate 11 may be provided on both surfaces.
- the Fe—Ni diffusion alloy plating layer 13 is a plating layer formed by alloying a Ni-plated steel sheet, and the Fe—Ni diffusion alloy plating layer 13 has a concentration gradient of Fe and Ni. Is formed.
- FIG. 2 is a view showing an analysis example of Ni and Fe in the plating layer depth direction by glow discharge emission analysis (GDS) of the Ni diffusion plated steel sheet according to the present embodiment. As shown in FIG. 2, in the Fe—Ni diffusion alloy plating layer 13, Ni shows the maximum concentration in the outermost layer of the Fe—Ni diffusion alloy plating layer 13, and the depth direction of the Fe—Ni diffusion alloy plating layer 13 Shows a monotonically decreasing concentration profile.
- the Ni intensity at a position of 0.5 ⁇ m from the outermost surface of the Fe—Ni diffusion alloy plating layer is x
- the Ni intensity is 0.1x (ie, The average value of the Ni change rate until it changes to 10% of the maximum Ni intensity) is a gradient of ⁇ 0.10x / ⁇ m or less (absolute value of 0.10x / ⁇ m or more).
- the average value of the Ni change rate until the Ni intensity changes from x to 0.1x is about ⁇ 0.23x / ⁇ m.
- Fe has a minimum concentration on the surface of the Fe—Ni diffusion alloy plating layer 13 and a concentration profile that monotonously increases in the depth direction of the Fe—Ni diffusion alloy plating layer 13.
- the change in Fe strength in the range of 1 ⁇ m and 2 ⁇ m from the surface of the Fe—Ni diffusion alloy plating layer 13 The average value of the rate is 0.02 y / ⁇ m or more.
- the average value of the change rate of Fe intensity in the range of 1 ⁇ m and 2 ⁇ m from the surface of the Fe—Ni diffusion alloy plating layer 13 is about 0.14 y / ⁇ m.
- the concentration gradient of Fe and Ni shown in FIG. 2 is the result of measuring the distribution of Fe and Ni in the depth direction by GDS with respect to the Fe—Ni diffusion alloy plating layer 13 of test number 2 in Examples described later. It is.
- GDA750 made by Rigaku was used as a GDS apparatus, and measurement was performed under the conditions of DC mode, voltage: 900 V, current: 20 mA, Ar pressure: 3 hPa, and measurement time: 200 seconds.
- the depth sputtered for 200 seconds was measured with a micrometer, and the sputtering depth per hour was calculated. At this time, the sputtering rate was calculated on the assumption that there was no change from the initial stage to 200 seconds.
- the Ni diffusion plated steel sheet 1 according to the present embodiment can be used as a material for various battery containers (battery containers) such as an alkaline manganese dry battery, a lithium ion battery, a nickel metal hydride battery, etc.
- battery containers battery containers
- the Fe—Ni diffusion alloy plating layer 13 is provided on one side of the base steel plate 11, the base steel plate 11 is formed on the side that becomes the outer surface of the battery container by press forming.
- the Fe—Ni diffusion alloy plating layer 13 is preferably provided.
- a base steel plate 11 of the Ni diffusion plated steel plate 1 according to the present embodiment is an Al-killed steel base steel plate, and is C: 0.005 to 0.250%, Si: 0.1% in mass%. Mn: 0.05 to 0.90%, P: 0.025% or less, S: 0.015% or less, sol. Al: 0.003 to 0.100%, N: 0.0070% or less, B: 0 to 0.0050%, with the balance being Fe and impurities.
- C is an element that greatly affects the crystal grain size and formability of the steel sheet.
- C advantageous texture as moldability contains less is easily formed, it is possible to increase the average plastic strain ratio r m as defined by the formula (I), refining the ferrite crystal grains It becomes difficult to cause rough skin in can processing. Such rough skin becomes prominent when the C content is less than 0.005%. Therefore, in the base material steel plate 11 according to the present embodiment, the C content is set to 0.005% or more.
- the C content is preferably 0.010% or more, and more preferably 0.020% or more.
- the C content is 0.250% or less.
- the content of C is preferably 0.200% or less, more preferably 0.100% or less, and still more preferably 0.060% or less.
- Si silicon
- Si silicon
- the Si content is 0.1% or less.
- the Si content is preferably 0.05% or less, more preferably 0.02% or less, and still more preferably 0.01% or less.
- the lower limit of the Si content is not particularly defined, but may be set to 0.001% or more from the viewpoint of desiliconization cost.
- Mn manganese
- S sulfur
- the Mn content is set to 0.05% or more.
- the Mn content is preferably 0.10% or more, and more preferably 0.15% or more.
- the Mn content is set to 0.90% or less.
- the Mn content is preferably 0.70% or less, more preferably 0.50% or less, and still more preferably 0.35% or less.
- P phosphorus
- P is contained as an impurity in the base material steel plate 11. Since P is an element contributing to strength, 0.025% may be contained in the base material steel plate 11 at the upper limit. However, since P is an element that embrittles steel and impairs workability, when the strength is not secured by P, the content of P is preferably 0.020% or less, more preferably, It is 0.012% or less, More preferably, it is 0.010% or less. From the viewpoint of toughness and workability, the P content is preferably a lower value. The lower limit of the P content is not particularly defined, but may be set to 0.005% or more from the viewpoint of dephosphorization cost.
- S sulfur
- S sulfur
- the base material steel plate 11 the S content is set to 0.025% or less.
- the S content is preferably 0.015% or less, and more preferably 0.010% or less. The smaller the S content, the better.
- the lower limit value of S is preferably about 0.0003%.
- Al (aluminum) is an element necessary for deoxidation of steel, and is also an element that suppresses age hardening by fixing solute N in steel as AlN.
- the Al content needs to be 0.005% or more.
- the Al content is preferably 0.015% or more.
- the Al content is 0.030% or more.
- the Al content is set to 0.100% or less.
- the Al content is preferably 0.070% or less, more preferably 0.060% or less, and still more preferably 0.050% or less.
- Al is sol. Al (acid-soluble Al) is meant.
- N nitrogen
- nitrogen is an element inevitably contained in steel.
- N is an element that age hardens the steel, reduces the press formability of the cold-rolled steel sheet, and generates stretcher strain.
- B when B is contained in the steel, N is combined with B to form a nitride, whereby age hardening due to solute N is suppressed.
- the N content is set to 0.0070% or less.
- the N content is preferably 0.0040% or less, and more preferably 0.0033% or less.
- the N content is preferably as low as possible. However, from the viewpoint of denitrification cost, the N content is preferably 0.0005% or more. In the present embodiment, when B is not contained in the steel, the content of N is set to 0.0020% or more when AlN is actively precipitated to refine the crystal grains. Is preferred.
- B (boron) is an optional additive element in the present embodiment. Therefore, the lower limit value of the B content is 0%.
- B is an effect of improving the r value (Rankford value) by texture control, an effect of bringing in-plane anisotropy ⁇ r (anisotropy of r value) defined by the following formula (101) close to 0, and AlN It is an element that exhibits effective effects such as the effect of fixing solid solution N that cannot be fixed as BN, reducing the aging property, and the effect of refining crystal grains.
- the B content is preferably 0.0005% or more, and more preferably 0.0010% or more.
- content of B exceeds 0.0050%, the various effects described above are saturated, and defects such as generation of surface defects may occur. For this reason, content of B shall be 0.0050% or less.
- the upper limit of the B content is preferably 0.0030%, and more preferably 0.0020%.
- the mass% ratio B / N between B and N is preferably in the range of 0.4 to 2.5.
- the remainder of the chemical composition is composed of Fe and impurities.
- an impurity means the thing mixed from the ore as a raw material, a scrap, or a manufacturing environment, when manufacturing steel materials industrially.
- the impurities include Cu, Ni, Cr, and Sn.
- the preferred contents of these elements are Cu: 0.5% or less, Ni: 0.5% or less, Cr: 0.3% or less, and Sn: 0.05% or less.
- the base material steel plate 11 is a cold-rolled steel plate.
- the crystal grain size number of the ferrite grains (that is, the ferrite grain size number) is 11.0 or more.
- the grain size number of the ferrite grains in the base steel plate 11 is preferably 11.2 or more.
- the upper limit of the crystal grain size number of the ferrite grains in the base steel plate 11 is not particularly specified, but it is often difficult to make the grain size number greater than 14.5.
- the crystal grain size number of the ferrite grain in this embodiment means the crystal grain size number of the ferrite grain based on JIS G 0551 (2013).
- the particle size number is defined as the value of G calculated by the following formula (151) using the average number of crystal grains m per 1 mm 2 of the cross section of the test piece. The value of can be positive, zero, or negative.
- the crystal grain size number of the ferrite grains is a value of G calculated by the above formula (151) using the average number of ferrite grains m per 1 mm 2 in cross section of the test piece.
- a large crystal grain size number means that the average number of crystal grains m per 1 mm 2 of the cross section of the test piece is large, and that the ferrite grains are refined. means.
- the crystal grain size number of the ferrite grains as described above can be measured in accordance with the method defined in JIS G 0551 (2013). For example, it is described in item 7.2 of JIS G 0551 (2013). It is possible to make a measurement by the comparative method described. More specifically, in a cross section parallel to the rolling direction (L direction) of the base steel plate 11, from the position of the depth of 1/4 of the plate thickness to the depth of 3/4 of the plate thickness in the thickness direction of the L cross section. By observing with the above-mentioned comparative method in the region of the range, the grain size number of the ferrite grains can be measured.
- Fe-Ni diffusion alloy plating layer 13 Next, the Fe—Ni diffusion alloy plating layer 13 according to this embodiment will be described in detail.
- the Fe—Ni diffusion alloy plating layer 13 included in the Ni diffusion plated steel sheet 1 according to the present embodiment is formed by Fe—Ni diffusion alloy plating over the entire thickness (in other words, the Fe—Ni diffusion alloy plating layer 13 of the Fe—Ni diffusion alloy plating layer 13). Fe has diffused to the outermost layer). Fe—Ni diffusion alloy plating is more base than pure Ni. Therefore, cracks (defects) that reach the base steel plate 11 exist in the Fe—Ni diffusion alloy plating layer 13, and the corrosion battery is between the Fe—Ni diffusion alloy plating layer 13 and Fe of the base steel plate 11. Even if is formed, the electromotive force is small. For this reason, the Fe—Ni diffusion alloy plating layer 13 has a feature that the corrosion from the defective portion hardly proceeds.
- the Ni adhesion amount of the Fe—Ni diffusion alloy plating layer 13 is in the range of 9.0 to 20 g / m 2 .
- the amount of Ni adhesion of the Fe—Ni diffusion alloy plating layer (the amount of Ni adhesion of the Ni plating before alloying treatment by thermal diffusion) is less than 9.0 g / m 2 (that is, the thickness of the Ni plating layer after plating is , Generally less than 1.0 ⁇ m) is also feasible in the prior art and is outside the scope of the present invention.
- the Ni adhesion amount of the Fe—Ni diffusion alloy plating layer 13 is 9.0 g / m 2 or more, which means that the thickness of the Ni plating layer after electroplating is approximately 1.0 ⁇ m or more. Means.
- the Ni adhesion amount is preferably 10 g / m 2 or more, more preferably 11 g / m 2 or more.
- the Ni adhesion amount of the Fe—Ni diffusion alloy plating layer 13 exceeds 20 g / m 2 , ferrite grains will be coarsened even if an electroplating method as described in detail below is used.
- the Ni adhesion amount of the Fe—Ni diffusion alloy plating layer 13 is set to 20 g / m 2 or less. In the present embodiment, the Ni adhesion amount of the Fe—Ni diffusion alloy plating layer 13 is preferably 15 g / m 2 or less.
- the adhesion amount of Ni in the Fe—Ni diffusion alloy plating layer 13 is determined by a method in which the plating layer is dissolved in an acid (for example, concentrated hydrochloric acid) and analyzed by ICP (Inductively Coupled Plasma) emission spectroscopy. It can be specified.
- an acid for example, concentrated hydrochloric acid
- ICP Inductively Coupled Plasma
- the Fe concentration Cs of outermost layer is in the range of 10 to 55 mass%.
- the Fe concentration Cs of the outermost layer is preferably 15% by mass or more, more preferably 20% by mass or more.
- the Fe concentration Cs of the outermost layer is preferably 50% by mass or less.
- an oxide film tends to grow on the surface layer of the Fe—Ni diffusion alloy plating layer 13, and the conductivity may be lowered.
- the Fe concentration Cs of the outermost layer is more preferably 45% by mass or less, and further preferably 43% by mass or less.
- the Fe concentration Cs of the outermost layer of the Fe—Ni diffusion alloy plating layer 13 can be measured using Auger Electron Spectroscopy (AES).
- AES Auger Electron Spectroscopy
- Changes in Fe concentration (Fe concentration profile) in the cross section of the Fe—Ni diffusion alloy plating layer 13 can also be measured using AES.
- argon ion etching in the AES apparatus is performed in a thickness of 50 nm from the surface layer of the sample in terms of SiO 2.
- the portion corresponding to is subjected to argon ion etching to remove the processed layer generated by the polishing process.
- line analysis in the thickness direction using an AES apparatus is performed.
- the Fe—Ni diffusion alloy plating layer 13 according to this embodiment has been described in detail.
- FIG. 3 is a flowchart showing an example of the flow of the method for manufacturing the Ni diffusion plated steel sheet according to the present embodiment.
- the Al-killed steel-based cold-rolled steel sheet is pre-cleaned, for example, by Ni electroplating. It is preferable to perform Ni plating and then perform continuous annealing. This is because it is rational because recrystallization of the raw steel plate and Fe—Ni alloying can be performed simultaneously in the continuous annealing process. Based on such an idea, a preferable method for producing a Ni diffusion-plated steel sheet, which will be described in detail below, includes steps as shown in FIG.
- the manufacturing method of the Ni diffusion plated steel sheet according to the present embodiment is a hot rolling process in which a slab having the above chemical components is hot-rolled to form a hot-rolled steel sheet ( Step S101), a cold rolling step (step S103) in which the obtained hot-rolled steel sheet is cold-rolled to form a cold-rolled steel sheet, and the obtained cold-rolled steel sheet is made of Ni using a high chloride bath.
- a Ni plating step for performing plating (Step S105) and an annealing / alloying step (Step S107) for performing annealing and alloying treatment by heat-treating the obtained Ni-plated steel sheet are included.
- the steelmaking conditions for obtaining the slab to be subjected to the hot rolling step are particularly limited as long as the steel having chemical components as described above can be melted to form a slab. It is not a thing and what is necessary is just to utilize a normal method suitably.
- the slab obtained by such a method (Al-killed steel slab) is subjected to hot rolling as described in detail below.
- the hot rolling process (step S101) is a process in which a slab having a predetermined chemical composition (Al-killed steel slab) is hot-rolled to obtain a hot-rolled steel sheet.
- a hot rolling step is an important step for bringing the crystal grains of the base material steel plate 11 in the Ni diffusion plated steel plate into a desired state.
- the slab is heated to 1000 ° C. or higher (preferably within a range of 1050 to 1300 ° C.), and finish rolling is performed at a temperature within a range of Ar 3 point to 950 ° C. It is preferable to cool it later and wind it up to form a hot-rolled steel strip.
- the heating temperature is less than 1000 ° C., it may be difficult to ensure the lower limit (ie, Ar3 point) of the temperature in finish rolling (finish rolling temperature), and the heating temperature exceeds 1300 ° C. In some cases, the oxide formed on the surface of the slab increases, which may cause surface defects.
- the finish rolling temperature is less than the Ar3 point, the ⁇ -region rolling is performed, so that the texture changes greatly and the earring resistance of the Ni diffusion plated steel sheet may be lowered.
- the finish rolling temperature exceeds 950 ° C., the crystal grains of the hot-rolled steel sheet are coarsened, and good earring resistance and fine ferrite grain size may not be obtained as a cold-rolled steel sheet.
- the steel sheet is rapidly cooled (for example, within 3 seconds) after finishing rolling in the above temperature range is completed.
- the coiling temperature of the obtained hot-rolled steel sheet is preferably in the range of 500 to 670 ° C.
- the winding temperature is preferably 600 ° C. or more.
- the coiling temperature exceeds 670 ° C., crystal grains after cold rolling and annealing described later may be coarse. If the coiling temperature is too high until it exceeds 720 ° C., cementite (Fe 3 C) may be coarsened when the C content is high.
- the coiling temperature is less than 500 ° C., quality variations occur in the coil width direction and the longitudinal direction, and the in-plane anisotropy ⁇ r defined by the above formula (101) may increase. growing.
- the steel sheet hot-rolled as described above is usually removed from the surface scale by pickling.
- a cold rolling process is a process of cold-rolling the hot-rolled steel sheet obtained by the hot-rolling process into a cold-rolled steel sheet.
- the cold rolling rate is preferably in the range of 85 to 92%, for example. If the cold rolling rate is less than 85%, ferrite crystal grains may be coarsened, which is not preferable. On the other hand, if the cold rolling rate exceeds 92%, the in-plane anisotropy of the r value may increase, which is not preferable from the viewpoint of securing earring resistance.
- a hot-rolled steel sheet material is used to prepare a steel sheet with a cold rolling rate changed in advance, and the cold rolling rate and ⁇ r defined by the above formula (101) are used. It is also possible to set the cold rolling rate so that the ⁇ r of the steel sheet becomes small. Even in such a case, the cold rolling rate obtained from the relationship between the cold rolling rate and ⁇ r substantially matches the range of the cold rolling rate described above.
- the finished plate thickness in the cold rolling process is preferably 1.20 mm or less.
- the finished plate thickness is preferably 0.08 mm or more, more preferably 0. .15 mm or more, more preferably 0.22 mm or more.
- the Ni plating described later may be applied to the steel sheet prior to the annealing process.
- the softening annealing of the steel plate base material and the Fe-Ni alloying of the Ni plating layer can be performed simultaneously, which is only rational. It is also advantageous from the viewpoint of energy saving.
- the Ni plating step (step S105) is a step of applying Ni plating to the obtained cold-rolled steel sheet using a high chloride bath.
- an electroplating method using a specific chloride bath that is, a high chloride bath
- a specific chloride bath that is, a high chloride bath
- the Fe concentration Cs of the outermost layer of the Fe—Ni diffusion alloy plating layer 13 can be set to 10% by mass or more while maintaining the state in which the crystal grains are miniaturized.
- Fe is added to the outermost layer of the Fe—Ni diffusion alloy plating layer 13. Can be diffused.
- the plating bath used for Ni electroplating is a high chloride bath using an electrolytic solution having a chloride ion concentration of 35.0 g / L or more and a Ni ion concentration of 40.0 g / L or more. is there.
- Ni plating using such a high chloride bath, Fe—Ni alloying in the annealing / alloying process is significantly promoted. The reason is not necessarily clear, but it is presumed that the internal stress generated in the electrodeposited film is affected.
- the chloride ion concentration in Ni plating bath shall be 35.0 g / L or more.
- concentration in Ni plating bath shall be 35.0 g / L or more.
- the chloride ion concentration is about 8.9 to 17.9 g / L (30 to 60 g / L in terms of nickel chloride hexahydrate).
- Ni electrodeposited from a Ni plating bath having a chloride ion concentration of 35.0 g / L or more has a large internal stress, and the Fe in the plating layer during annealing and alloying is large. Diffusion is fast.
- the ion concentration in the Ni plating bath is preferably 40.0 g / L or more, more preferably 50.0 g / L or more, and further preferably 60.0 g / L or more.
- the upper limit of the chloride ion concentration is not particularly limited, but from the viewpoint of the solubility of nickel chloride, the chloride ion concentration is preferably 150.0 g / L or less.
- the chloride ion concentration in the Ni plating bath is preferably 125.0 g / L or less, more preferably 110.0 g / L or less, and further preferably 100.0 g / L or less.
- Ni ion concentration in the Ni plating bath is 40.0 g / L or more from the viewpoint of securing current efficiency.
- the Ni ion concentration is preferably 60.0 g / L or more, more preferably 80.0 g / L or more.
- the upper limit of the Ni ion concentration is not particularly limited, but from the viewpoint of the solubility of nickel chloride, the Ni ion concentration is preferably 125.0 g / L or less, more preferably 100.0 g / L or less. is there.
- the concentration of sulfate ions in the Ni plating bath is not particularly limited, and may be a total chloride bath containing no sulfate ions, and the sulfate ion concentration is higher in chloride ions as in the Watts bath.
- the bath may be higher than the concentration.
- the boric acid concentration in the Ni plating bath is not particularly limited, and boric acid may be contained in the range of 15 to 60 g / L, as in the Watts bath. When the Ni plating bath contains 15 to 60 g / L of boric acid, the pH of the plating bath can be stabilized, which is preferable.
- the Ni plating bath may contain cations such as Na ions that do not precipitate from the aqueous solution, for example, as cations such as a supporting electrolyte.
- the pH of the Ni plating bath is not particularly limited as long as it is a weakly acidic region.
- the pH of the Ni plating bath is preferably 2.5 or more and 5.0 or less.
- the primary gloss additive represented by sodium saccharin has a function of relieving the internal stress of Ni plating, and therefore it is preferable not to add it positively.
- secondary gloss additives such as 1,4-butynediol have the effect of increasing the internal stress of Ni plating, but are proactively added because diffusion may be inhibited by eutectoid C. Preferably not.
- the temperature (bath temperature) of the Ni plating bath is not particularly limited, and the effect of the plating bath can be obtained by setting the temperature to a known temperature range. However, if the bath temperature is too low, the current efficiency may decrease or the stress may be relatively low. If the bath temperature is too high, the Ti basket filled with the Ni tip of the anode In addition, there is a possibility that the Ti plate of the base material of the insoluble anode (for example, an electrode in which a Ti base material is coated with IrO 2 or the like) is easily dissolved. Therefore, in order to operate more reliably, the bath temperature of the Ni plating bath is preferably 40 ° C. or higher and 60 ° C. or lower.
- the current density at the time of performing Ni electroplating is not specifically limited, The effect by the said plating bath can be acquired by setting it as the range of a well-known current density. However, if the current density is too low, the productivity may decrease, and if the current density is too high, the current efficiency may decrease or plating burn may occur. Therefore, in order to operate more reliably, the current density when performing Ni electroplating is preferably 5 A / dm 2 or more and 50 A / dm 2 or less. It should be noted that an LCC-H (Liquid Cushion Cell Horizontal) type plating cell that can smoothly supply ions by a high-speed flow [horizontal fluid-supported electrolytic cell, for example, Journal of the Japan Institute of Metals, Vol. 23, No. 6 , P.M. 541-543 (1984). ], Ni electroplating may be performed at a higher current density.
- LCC-H Liquid Cushion Cell Horizontal
- the annealing / alloying treatment step is a step of performing annealing and alloying treatment by heat-treating the obtained Ni-plated steel sheet.
- the annealing / alloying treatment process is a heat treatment process performed in accordance with predetermined heat treatment conditions, but is an annealing process in view of the base steel sheet, and in view of the plating layer. It is an alloying process.
- the heat treatment for annealing and alloying is preferably performed by continuous annealing rather than box annealing.
- box annealing there is a possibility that variations in crystal grain size and characteristics due to non-uniform temperature distribution in the coil may occur.
- box annealing the coiled steel sheet is heat-treated, so in the case of single-sided plating, the plated surface and the steel plate surface adhere to each other, and in the case of double-sided plating, the plated surfaces adhere to each other, thereby causing surface defects. It can happen.
- the soaking temperature is not less than the recrystallization temperature and not less than 670 ° C. and not more than 760 ° C. (however, less than Ac1 point).
- the soaking temperature is preferably 685 ° C. or higher, more preferably 690 ° C. or higher.
- the soaking temperature is preferably 740 ° C. or lower, more preferably 730 ° C. or lower.
- the soaking time is in the range of 5 to 180 seconds.
- the soaking time is preferably 15 seconds or longer, more preferably 20 seconds or longer.
- the soaking time is preferably 120 seconds or shorter, more preferably 50 seconds or shorter.
- the entire plating layer can be made an Fe—Ni diffusion alloy plating layer.
- the soaking temperature exceeds the Ac1 point when the C content is high, pearlite may precipitate in the cooling process, which is not preferable. Further, when the soaking temperature is less than 670 ° C., it may be difficult to make the Fe concentration Cs in the outermost layer of the plating layer 10 mass% or more even if the soaking time is 180 seconds. In this case, the recrystallization of the base material steel plate becomes insufficient, the average plastic strain ratio r m is also likely to deteriorate. On the other hand, when the soaking temperature exceeds 760 ° C., even if the soaking time is set to 5 seconds, the crystal grains become coarse and it may be difficult to secure the target grain size number.
- C in a solid solution state within the range of the soaking temperature may remain in the steel sheet as a solid solution C when the cooling rate after annealing is large, and may cause an age hardening phenomenon. It is possible to suppress such age hardening phenomenon by controlling the cooling rate after annealing. For example, when the content of C exceeds 0.10% by mass, if the cooling rate after annealing is set to 80 ° C./sec or less, the solid solution C is precipitated and fixed as Fe 3 C.
- the steel sheet that has been subjected to the above annealing / alloying treatment process may be further subjected to an overaging treatment in a temperature range of 400 to 550 ° C.
- an overaging treatment By performing such overaging treatment, the occurrence of stretcher strain can be more reliably prevented.
- temper rolling skin pass rolling
- the reduction ratio in temper rolling is preferably 0.5 to 10.0%, for example.
- yield point elongation may occur due to aging at room temperature.
- the rolling reduction exceeds 10.0%, the total elongation (ELongation: EL) is lowered, and the press formability (drawing workability) may be lowered.
- the temper rolling in which the rolling reduction is in the range of 0.5 to 10.0% is preferable because the generation of stretcher strain can be substantially suppressed and excellent press formability can be secured.
- by carrying out temper rolling within the range of a rolling reduction of 3.5% or less it is possible to produce a superior one by shape, and adjusting the yield strength by appropriately selecting the tempering degree. Is possible.
- the Ni diffusion plated steel sheet according to this embodiment is manufactured by the manufacturing process as described above.
- the thickness (final thickness) of the Ni diffusion plated steel sheet according to the present embodiment is preferably 1.20 mm or less, more preferably 0.80 mm or less, and further preferably 0.70 mm or less.
- the plate thickness (final plate thickness) of the Ni diffusion plated steel plate according to this embodiment is preferably 0.08 mm or more, more preferably 0.15 mm or more, and further preferably 0.22 mm or more.
- the sheet thickness of the hot-rolled steel sheet must be reduced, and in this case, the finishing temperature during the above hot rolling may not be ensured.
- Ni diffusion plated steel sheet according to the present invention will be specifically described with reference to Examples and Comparative Examples.
- Example shown below is only an example of the Ni diffusion plating steel plate concerning this invention, and the Ni diffusion plating steel plate concerning this invention is not limited to the example shown below.
- Ni plating is performed by electroplating on an unannealed Al-Killed steel plate (length 300 mm ⁇ width 20 mm) cold-rolled to 0.25 mm. After that, heat treatment simulating a continuous annealing line was performed. However, with respect to some test materials, cold-rolled steel plates that were previously annealed were used.
- Table shows the temperature conditions (SRT: heating temperature, FT: finishing temperature, CT: coiling temperature, unit: ° C) and the rolling rate (Red, unit:%) in the cold rolling process of each steel sheet. This is also shown in 1.
- Ni plating was performed by electroplating.
- the Ni plating bath used is summarized in Table 2 below.
- the pH of the plating bath was adjusted using basic nickel carbonate [Ni 4 CO 3 (OH) 6 (H 2 O) 4 ], and the plating bath temperature was 60 ° C. Common.
- Ni plates having a purity of 99.9% or more were used for the anodes, respectively, and the cathode current density was 20 A / dm 2 in common.
- the expression “high Cl bath” means “high chloride bath”.
- the Ni adhesion amount was measured using a scanning fluorescent X-ray analyzer ZSX Primus II manufactured by Rigaku after Ni plating.
- the steel plate subjected to Ni plating was subjected to a heat treatment (that is, annealing / alloying treatment) simulating a continuous annealing line in an atmosphere consisting of H 2 : 4% by volume and the balance N 2 .
- the plated steel sheet that has undergone such a heat treatment step was subjected to temper rolling with a rolling reduction of 1.8%.
- Ni plating baths used for Ni plating in each test example The types of Ni plating baths used for Ni plating in each test example, the amount of Ni plating deposited, and the annealing conditions (soaking temperature and soaking time) after plating are also shown in Table 3 below.
- the Fe concentration Cs of each Ni diffusion plated steel sheet was analyzed by AES in accordance with the above-described method, and the Fe concentration when the sum of Ni and Fe was set to 100% was calculated by mass%. The obtained results are also shown in Table 4.
- the AES apparatus used for the analysis is a PHI-610 scanning Auger electron spectrometer manufactured by PerkinElmer.
- the surface of the obtained sample is sputtered with Ar ions to a thickness of 10 nm in terms of SiO 2 to obtain a contamination layer (for example, an oxide layer) that may be formed on the surface layer of the Fe—Ni diffusion alloy plating layer. Etc.) was removed, and the composition of a region having a diameter of 800 ⁇ m was analyzed.
- the Ni diffusion plated steel sheets corresponding to the examples of the present invention showed excellent evaluation results in all of continuous pressability, corrosion resistance, and contact resistance values.
- the Ni diffusion plated steel sheet corresponding to the comparative example of the present invention is inferior in at least one of continuous pressability and corrosion resistance.
- the Fe—Ni diffusion alloy plating film itself was inferior in corrosion resistance despite satisfying the conditions of the present invention. This is presumably because the crystal grains of the base steel plate are coarsened (that is, the ferrite grain size number is less than 11.0), and the grain boundary cracking of the base material is likely to occur during forming and propagates to the plating layer.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Heat Treatment Of Sheet Steel (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
Abstract
Description
本願は、2018年4月13日に、日本に出願された特願2018-077883号に基づき優先権を主張し、その内容をここに援用する。
rm = (r0+2×r45+r90)/4 ・・・・・(I)
ただし、上記式(I)において、r0:圧延方向r値、r90:圧延直交方向r値、r45:45°方向r値であり、r値は、塑性歪比(Lankford値)である。
かかる知見に基づき完成された本発明の要旨は、以下の通りである。
(2)(1)に記載のNi拡散めっき鋼板は、前記Fe-Ni拡散合金めっき層の最表層のFe濃度Csが、15~40質量%であってもよい。
(3)(1)又は(2)に記載のNi拡散めっき鋼板は、容器の素材として用いられ、前記母材鋼板において、プレス成形により容器の外面となる側に、前記Fe-Ni拡散合金めっき層が設けられてもよい。
(4)本発明の別の一態様に係るNi拡散めっき鋼板の製造方法は、(1)に記載の化学組成を有する母材鋼板の少なくとも一方の表面上に、塩化物イオン濃度が35.0g/L以上であり、かつ、Niイオン濃度が40.0g/L以上であるNiめっき浴を用いて、電気めっきにより、付着量が9.0~20g/m2のNiめっき層を形成するNiめっき工程と、前記Niめっき工程後、670~760℃の温度範囲で、均熱時間5~180秒の熱処理を行って、前記Niめっき層の最表層のFe濃度Csを10~55質量%とする焼鈍・合金化処理工程と、を有する。
まず、図1A及び図1Bを参照しながら、本発明の実施形態に係るNi拡散めっき鋼板の全体構成について説明する。図1A及び図1Bは、本実施形態に係るNi拡散めっき鋼板の構造の一例を模式的に示した説明図である。
図2は、本実施形態に係るNi拡散めっき鋼板のグロー放電発光分析(GDS)によるめっき層深さ方向のNi、Feの分析例を示す図である。図2に示すように、Fe-Ni拡散合金めっき層13では、Niは、Fe-Ni拡散合金めっき層13の最表層で最大の濃度を示し、Fe-Ni拡散合金めっき層13の深さ方向に単調に減少する濃度プロファイルを示す。
このとき、Fe-Ni拡散合金めっき層13の深さ方向において、Fe-Ni拡散合金めっき層の最表面から0.5μmの位置におけるNi強度をxとしたとき、Ni強度が0.1x(即ち、Niの最大強度の10%の強度)に変化するまでのNi変化率の平均値は、-0.10x/μm以下(絶対値としては0.10x/μm以上)の勾配となる。図2に示す例では、Ni強度がxから0.1xに変化するまでのNi変化率の平均値は、約-0.23x/μmである。
このとき、Fe-Ni拡散合金めっき層13の表面から6μmの深さの位置におけるFe強度をyとしたとき、Fe-Ni拡散合金めっき層13の表面から1μmと2μmの範囲におけるFe強度の変化率の平均値は、0.02y/μm以上である。図2に示す例では、Fe-Ni拡散合金めっき層13の表面から1μmと2μmの範囲におけるFe強度の変化率の平均値は、約0.14y/μmである。
図2において、最表面の近傍は放電が不安定であるため、データを除いて示している。なお、図2の結果は、Fe、Ni各元素について測定された強度を示しており、組成(質量%)を直接的に示すものではないが、Fe―Niの相互拡散によって生じた、各元素の濃度勾配の傾向を示す。
続いて、本実施形態に係るNi拡散めっき鋼板1における母材鋼板11について、詳細に説明する。
以下では、本実施形態に係る母材鋼板11の化学組成について、詳細に説明する。
なお、以下の化学組成に関する説明において、「%」の表記は、断わりのない限りは、「質量%」を意味する。
C(炭素)は、鋼板の結晶粒度及び成形性に非常に大きな影響を及ぼす元素である。Cの含有量が少ないほど成形性に有利な集合組織が形成されやすくなり、上記式(I)で規定される平均塑性歪比rmを大きくすることができるが、フェライト結晶粒を微細化することが困難となり、缶加工においては肌荒れを招きやすくなる。かかる加工時の肌荒れは、Cの含有量が0.005%未満となる場合に顕著となる。従って、本実施形態に係る母材鋼板11では、Cの含有量を、0.005%以上とする。Cの含有量は、好ましくは、0.010%以上であり、より好ましくは、0.020%以上である。
一方、Cの含有量が増加すると、フェライト結晶粒の微細化は容易となるが、鋼板の強度が上昇して、絞り加工性の低下を招きやすい。また、焼鈍温度が二相域になると、パーライトが析出して、加工性が低下する場合がある。かかる加工性の低下は、Cの含有量が0.250%を超えた場合に顕著となる。従って、本実施形態に係る母材鋼板11では、Cの含有量を0.250%以下とする。Cの含有量は、好ましくは、0.200%以下であり、より好ましくは、0.100%以下であり、更に好ましくは、0.060%以下である。
本実施形態に係る母材鋼板11において、Si(ケイ素)は、鋼中に不純物として含有される。Siの含有量が0.1%を超える場合には、表面処理性を低下させる。従って、本実施形態に係る母材鋼板11において、Siの含有量は、0.1%以下とする。Siの含有量は、好ましくは0.05%以下であり、より好ましくは0.02%以下、さらに好ましくは0.01%以下である。
Si含有量の下限値は特に定められないが、脱珪コストの観点から、0.001%以上と定めてもよい。
Mn(マンガン)は、母材鋼板11中に含まれる不純物であるS(硫黄)に起因する熱間圧延中の赤熱脆性を防止する上で有効な元素である。かかる赤熱脆性の防止効果は、Mnの含有量を0.05%以上とすることで発現させることができる。従って、本実施形態に係る母材鋼板11では、Mnの含有量を、0.05%以上とする。Mnの含有量は、好ましくは、0.10%以上であり、より好ましくは、0.15%以上である。
一方、Mnの含有量が過大になると、鋼板が硬質化して、深絞り性が低下するとともに、連続鋳造中にMnSが析出して熱間脆性を引き起こしやすくなる。これらの現象は、Mnの含有量が0.90%を超える場合に顕著となる。従って、本実施形態に係る母材鋼板11では、Mnの含有量を0.90%以下とする。Mnの含有量は、好ましくは0.70%以下であり、より好ましくは、0.50%以下であり、更に好ましくは、0.35%以下である。
P(リン)は、母材鋼板11中に不純物として含有される。Pは、強度に寄与する元素であるため、母材鋼板11中に、0.025%を上限に含有させてもよい。ただし、Pは、鋼を脆化させて、加工性を損なう元素でもあるため、Pによる強度確保を意図しない場合は、Pの含有量は、好ましくは、0.020%以下、より好ましくは、0.012%以下、さらに好ましくは、0.010%以下である。靭性及び加工性の観点からは、Pの含有量は、より低い値となることが好ましい。
P含有量の下限値は特に定められないが、脱燐コストの観点から、0.005%以上と定めてもよい。
S(硫黄)は、母材鋼板11中に不純物として含有される。Sの含有量が0.025%を超える場合には、熱間圧延中に赤熱脆性を引き起こしたり、連続鋳造中にMnSが析出して熱間脆性を引き起こし、鋳片割れを招いたりする。そこで、本実施形態に係る母材鋼板11では、Sの含有量を0.025%以下とする。Sの含有量は、好ましくは、0.015%以下、より好ましくは、0.010%以下である。
Sの含有量は、少なければ少ないほど好ましい。ただし、脱硫コストの観点からは、Sの下限値は、0.0003%程度とすることが好ましい。
Al(アルミニウム)は、鋼の脱酸に必要な元素であり、また、AlNとして鋼中の固溶Nを固定して、時効硬化を抑制する元素でもある。これらの効果を得るためには、Alの含有量を0.005%以上とする必要がある。特に、時効性に対して厳しい用途の場合には、Alの含有量を、0.015%以上とすることが好ましい。また、AlのN固定効果を積極的に得ようとする場合(例えば、鋼がB(ホウ素)を含有することなく、Al以外に固溶Nを固定する合金元素が存在しない場合)には、Alの含有量を0.030%以上とすることが好ましい。
一方、Alの含有量が多すぎると、アルミナクラスターなどに起因する表面欠陥の発生頻度が急増する。かかる表面欠陥の発生頻度は、Alの含有量が0.100%を超えた場合に急増するため、本実施形態に係る母材鋼板11では、Alの含有量を、0.100%以下とする。Alの含有量は、好ましくは、0.070%以下、より好ましくは、0.060%以下、さらに好ましくは0.050%以下である。なお、本実施形態において、Alとは、sol.Al(酸可溶Al)を意味する。
N(窒素)は、鋼中に不可避的に含有される元素である。Nは、鋼を時効硬化させる元素であり、冷延鋼板のプレス成形性を低下させ、ストレッチャーストレインを発生させる。本実施形態に係る母材鋼板11において、鋼中にBが含有される場合には、NはBと結合して窒化物を形成することにより、固溶Nによる時効硬化は抑制される。しかしながら、Nの含有量が0.0070%を超える場合には、固溶Nによる時効硬化が生じやすくなる。従って、本実施形態に係る母材鋼板11では、Nの含有量を0.0070%以下とする。N含有量は、好ましくは、0.0040%以下、より好ましくは、0.0033%以下である。
なお、Nの含有量は、なるべく低い値であることが好ましい。ただし、脱窒コストの観点からは、Nの含有量は、0.0005%以上であることが好ましい。なお、本実施形態において、鋼中にBが含有されない場合において、AlNを積極的に析出させて結晶粒の微細化を図る際には、Nの含有量を、0.0020%以上とすることが好ましい。
B(ホウ素)は、本実施形態においては、任意添加元素である。そのため、B含有量の下限値は0%である。Bは、集合組織制御によりr値(Lankford値)を向上させる効果、以下の式(101)で定義される面内異方性Δr(r値の異方性)を0に近づける効果、AlNとして固定しきれない固溶NをBNとして固定し、時効性を低減する効果、及び、結晶粒を微細化させる効果等の有効な効果を奏する元素である。AlによるN固定の効果があまり期待できない場合(例えば、鋼中のAl濃度が0.030%未満である場合や、熱間圧延工程前の鋳片加熱温度が1120℃を超える製造条件の場合等)においては、Bの含有量を、0.0005%以上とすることが好ましく、0.0010%以上とすることがより好ましい。
ただし、Bの含有量が、0.0050%を超える場合には、上記の各種効果は飽和するとともに、表面欠陥の発生等の不具合を生じる場合がある。このため、Bの含有量は、0.0050%以下とする。なお、Bの含有量の上限値は、好ましくは、0.0030%であり、より好ましくは、0.0020%である。なお、Bによって固溶Nを十分固定するためには、BとNの質量%比率B/Nを、0.4~2.5の範囲とすることが好ましい。
ただし、上記式(101)において、
r0:圧延方向r値
r90:圧延直交方向r値
r45:45°方向r値
r値:塑性歪比(Lankford値)
である。
本実施形態に係る母材鋼板11において、化学組成の残部は、Fe及び不純物からなる。ここで、本実施形態において、不純物とは、鉄鋼材料を工業的に製造する際に、原料としての鉱石、スクラップ、又は、製造環境などから混入するものを意味する。上記不純物として、例えば、Cu、Ni、Cr及びSn等を挙げることができる。これらの元素の好ましい含有量は、Cu:0.5%以下、Ni:0.5%以下、Cr:0.3%以下、及びSn:0.05%以下である。
本実施形態に係る母材鋼板11において、フェライト粒の結晶粒度番号(すなわち、フェライト粒度番号)は、11.0以上である。結晶粒度番号が11.0未満である場合、缶形状に成形する際に、缶胴壁表面に肌荒れが発生しやすく、好ましくない。母材鋼板11におけるフェライト粒の結晶粒度番号は、好ましくは、11.2以上である。一方、母材鋼板11におけるフェライト粒の結晶粒度番号の上限は、特に規定するものではないが、結晶粒度番号14.5超とすることは困難な場合が多い。
続いて、本実施形態に係るFe-Ni拡散合金めっき層13について、詳細に説明する。
本実施形態において、Fe-Ni拡散合金めっき層13のNi付着量は、9.0~20g/m2の範囲内である。Fe-Ni拡散合金めっき層のNi付着量(熱拡散による合金化処理前のNiめっきのNi付着量)が9.0g/m2未満であるもの(すなわち、めっき後のNiめっき層の厚みが、概ね1.0μm未満であるもの)は、多くの場合、従来の技術においても実現可能であり、本発明の範囲外とする。従って、本実施形態において、Fe-Ni拡散合金めっき層13のNi付着量が9.0g/m2以上であることは、電気めっき後のNiめっき層の厚みが概ね1.0μm以上であることを意味する。Ni付着量は、好ましくは10g/m2以上、より好ましくは11g/m2以上とする。
一方、Fe-Ni拡散合金めっき層13のNi付着量が20g/m2を超える場合には、以下で詳述するような電気めっき法を用いたとしても、フェライト結晶粒の粗大化を招くことなく、Fe-Ni拡散合金めっき層13の表面まで十分なFe-Ni合金化を進行させることが困難となる。従って、本実施形態に係るFe-Ni拡散合金めっき層13のNi付着量は、20g/m2以下とする。本実施形態において、Fe-Ni拡散合金めっき層13のNi付着量は、好ましくは15g/m2以下である。
上記のように、本実施形態に係るFe-Ni拡散合金めっき層13では、めっき層の最表層までFeが拡散しており、最表層のFe濃度を規定することができる。本実施形態に係るFe-Ni拡散合金めっき層13において、最表層のFe濃度Csは、10~55質量%の範囲内である。最表層のFe濃度Csが10質量%未満である場合には、Fe-Ni拡散合金めっき層13の摺動性が不十分であり、プレス加工時に金型との凝着等が発生しやすくなるため、好ましくない。最表層のFe濃度Csは、好ましくは、15質量%以上であり、より好ましくは20質量%以上である。
一方、最表層のFe濃度Csが55質量%を超える場合には、Fe-Ni拡散合金めっき層13そのものから錆が発生し易くなるため、好ましくない。最表層のFe濃度Csは、好ましくは50質量%以下である。本実施形態に係るNi拡散めっき鋼板1が置かれる環境によっては、Fe-Ni拡散合金めっき層13の表層に酸化被膜が成長しやすくなり、導電性が低下する可能性が生じうる。表層のFe濃度Csを50質量%以下とすることで、上記のような酸化被膜の成長を抑制して、導電性の低下を未然に抑制することが可能となる。最表層のFe濃度Csは、より好ましくは、45質量%以下、さらに好ましくは43質量%以下である。
続いて、図3を参照しながら、本実施形態に係るNi拡散めっき鋼板の製造方法について、詳細に説明する。図3は、本実施形態に係るNi拡散めっき鋼板の製造方法の流れの一例を示した流れ図である。
熱間圧延工程(ステップS101)は、所定の化学成分を有する鋳片(Al-killed鋼系の鋳片)を熱間圧延して、熱延鋼板とする工程である。かかる熱間圧延工程は、Ni拡散めっき鋼板における母材鋼板11の結晶粒を所望の状態とするために重要な工程である。
冷間圧延工程(ステップS103)は、熱間圧延工程により得られた熱延鋼板を冷間圧延して、冷延鋼板とする工程である。
かかる冷間圧延工程において、冷間圧延率は、例えば、85~92%の範囲内であることが好ましい。冷間圧延率が85%未満となる場合には、フェライト結晶粒の粗大化を招くおそれがあるため、好ましくない。一方、冷間圧延率が92%を超える場合には、r値の面内異方性が増大するおそれがあるため、耐イヤリング性確保の観点で好ましくない。
Niめっき工程(ステップS105)は、得られた冷延鋼板に対して、高塩化物浴を用いてNiめっきを施す工程である。
ここで、Ni電気めっきに用いるめっき浴は、塩化物イオン濃度が35.0g/L以上であり、かつ、Niイオン濃度が40.0g/L以上の電解液を用いた、高塩化物浴である。このような高塩化物浴を用いてNiめっきを行うことで、焼鈍・合金化工程でのFe-Niの合金化が顕著に促進される。その理由は必ずしも明確ではないが、電析皮膜に発生する内部応力が影響していると推察される。
電気めっきに用いる、高塩化物浴の具体的な組成であるが、Niめっき浴中における塩化物イオン濃度は、35.0g/L以上とする。Niめっきで広く用いられているWatts(ワット)浴では、塩化物イオン濃度が8.9~17.9g/L(塩化ニッケル・6水和物換算で、30~60g/L)程度である。Watts浴から電析したNiと比較して、塩化物イオン濃度が35.0g/L以上のNiめっき浴から電析したNiは、内部応力が大きく、焼鈍・合金化時にめっき層内のFeの拡散が早い。Niめっき浴中におけるNiイオン濃度は、低すぎると電流効率が低下し、十分な生産性が得られなかったり、相対的に内部応力が小さくなったりすることがあるため、Niめっき浴の塩化物イオン濃度は、好ましくは40.0g/L以上であり、より好ましくは50.0g/L以上であり、さらに好ましくは60.0g/L以上である。
塩化物イオン濃度の上限は、特に限定されないが、塩化ニッケルの溶解度の観点から、塩化物イオン濃度は150.0g/L以下とすることが好ましい。Niめっき浴中における塩化物イオン濃度は、好ましくは125.0g/L以下であり、より好ましくは110.0g/L以下であり、さらに好ましくは100.0g/L以下である。
Niめっき浴におけるNiイオン濃度は、電流効率確保の観点から、40.0g/L以上とする。Niイオン濃度は好ましくは60.0g/L以上、より好ましくは80.0g/L以上である。Niイオン濃度の上限については、特に限定するものではないが、塩化ニッケルの溶解度の観点から、Niイオン濃度は125.0g/L以下とすることが好ましく、より好ましくは100.0g/L以下である。
なお、高速な流れによりイオン供給をスムーズに行うことができる、LCC-H(Liquid Cushion Cell Horizontal)型のめっきセル[横型流体支持電解槽、例えば、日本金属学会会報、第23巻、第6号、P.541~543(1984)を参照。]を使用する場合には、より高い電流密度でNi電気めっきを実施してもよい。
焼鈍・合金化処理工程(ステップS107)は、得られたNiめっき鋼板を熱処理することで、焼鈍及び合金化処理を施す工程である。かかる焼鈍・合金化処理工程により、母材鋼板を再結晶させるとともに、母材鋼板中のFeとNiめっき層のNiとを相互拡散させることで、Niめっき層をFe-Ni拡散合金めっき層へと変化させる。本実施形態に係る焼鈍・合金化処理工程は、所定の熱処理条件に則して実施される熱処理工程であるが、母材鋼板の観点から鑑みれば焼鈍工程であり、めっき層の観点から鑑みれば合金化処理工程となっている。
均熱温度は、好ましくは685℃以上であり、より好ましくは690℃以上である。
均熱温度は、好ましくは740℃以下であり、より好ましくは730℃以下である。
均熱時間は、好ましくは15秒以上であり、より好ましくは20秒以上である。
均熱時間は、好ましくは120秒以下であり、より好ましくは50秒以下である。
ここで、本実施形態に係るNi拡散めっき鋼板の板厚(最終板厚)は、1.20mm以下であることが好ましく、より好ましくは0.80mm以下、さらに好ましくは0.70mm以下である。最終板厚が大きい場合は、冷間圧延時の圧下率を確保することが困難となる可能性があり、優れた絞り加工性が得られにくくなる場合がある。また、本実施形態に係るNi拡散めっき鋼板の板厚(最終板厚)は、0.08mm以上であることが好ましく、より好ましくは0.15mm以上、さらに好ましくは0.22mm以上である。最終板厚が小さい場合は、熱延鋼板の板厚を薄くしなければならず、この場合、上述の熱間圧延時の仕上げ温度を確保できないことがある。
ここで、以下に示す全ての実施例及び比較例においては、0.25mmに冷間圧延された未焼鈍のAl-Killed系鋼板(長さ300mm×幅20mm)に対し、電気めっきによりNiめっきを施し、その後、連続焼鈍ラインをシミュレートした熱処理を施した。但し、一部の試験材に関しては、予め焼鈍を行った冷延鋼板を用いた。
各Ni拡散めっき鋼板のL断面(圧延方向及び板厚方向に平行な断面)にて、光学顕微鏡観察を行い、冷延鋼板の組織を特定した。その結果、各Ni拡散めっき鋼板の組織は、いずれもフェライト単相組織またはフェライトを主体とする組織であった。更に、各試験番号のNi拡散めっき鋼板のフェライト粒の結晶粒度番号を、L断面の厚み方向に、板厚の1/4の深さの位置から板厚の3/4の深さの範囲の部位で観察し、JIS G 0552(2013)に準拠して、上述の方法で求めた。得られた結果を表4に記載した。
各Ni拡散めっき鋼板のFe濃度Csを、上述の方法に則してAESにより分析し、NiとFeの和を100%とした場合のFe濃度を質量%で算定した。得られた結果を、表4に併記した。分析にあたって、使用したAES装置は、パーキンエルマー社製、PHI-610走査型オージェ電子分光装置である。分析に当たっては、得られた試料の表面を、ArイオンによりSiO2換算で10nmスパッタして、Fe-Ni拡散合金めっき層の表層に形成されている可能性のある汚染層(例えば、酸化物層等)を除去した後、直径800μmの領域の組成を分析した。
各Ni拡散めっき鋼板に関し、加工が4段である多段プレス成型にて、円筒絞り加工での連続プレス性を評価した。具体的には、プレス油に日本工作油製No.641Rを用い、ブランク径52mmφでサンプルを打ち抜き、4段目までで高さ:36mm、直径:16mmに絞った。このプレス加工を同一金型で連続して100回行った後、得られた100個の絞り成形品の表面をそれぞれ目視観察して、全ての絞り成形品について疵が視認されないものをVeryGood、軽微な疵のみが認められたものをGood、疵の目立ったものをBadとして評価した。なお、連続100回のプレス加工において、プレス金型へのめっき金属の凝着があっても、凝着物を除去せずにプレス加工を継続した。得られた結果を、表4に併記した。
上記の連続プレス試験で得られた100缶目の絞り成形品について、有機溶剤で脱脂した後、1hrの塩水噴霧試験(JIS Z 2371)に供し、赤錆発生状況を確認した。赤錆が発生しなかったものをGood、赤錆が発生したものをBadとして評価した。得られた結果を、表4に併記した。
各Ni拡散めっき鋼板を、85℃、相対湿度85%の環境に2週間保持した後、山崎精機研究所製電気接点シュミレータCRS-1を用い、荷重20gにおける鋼板サンプルの接触抵抗を測定した。接触抵抗の測定値が30mΩ未満であったものをVeryGoodとし、30mΩ以上50mΩ未満であったものをGoodとし、50mΩ以上であったものをBadとして評価した。得られた結果を、以下の表4に併記した。
11 母材鋼板
13 Fe-Ni拡散合金めっき層
Claims (4)
- 母材鋼板と;
前記母材鋼板の少なくとも片面上に位置するFe-Ni拡散合金めっき層と;を備え、
前記Fe-Ni拡散合金めっき層のNi付着量が、9.0~20g/m2であり、
前記Fe-Ni拡散合金めっき層の最表層のFe濃度Csが、10~55質量%であり、
前記母材鋼板の化学組成は、質量%で、
C:0.005~0.250%、
Si:0.1%以下、
Mn:0.05~0.90%、
P:0.025%以下、
S:0.025%以下、
sol.Al:0.005~0.100%、
N:0.0070%以下、
B:0~0.0050%
を含有し、
残部がFe及び不純物からなり、
前記母材鋼板のJIS G 0551(2013)で規定されるフェライト粒度番号が、11.0以上である
ことを特徴とするNi拡散めっき鋼板。 - 前記Fe-Ni拡散合金めっき層の最表層のFe濃度Csが、15~40質量%であることを特徴とする請求項1に記載のNi拡散めっき鋼板。
- 容器の素材として用いられ、
前記母材鋼板において、プレス成形により容器の外面となる側に、前記Fe-Ni拡散合金めっき層が設けられる
ことを特徴とする請求項1又は2に記載のNi拡散めっき鋼板。 - 請求項1に記載の化学組成を有する母材鋼板の少なくとも一方の表面上に、塩化物イオン濃度が35.0g/L以上であり、かつ、Niイオン濃度が40.0g/L以上であるNiめっき浴を用いて、電気めっきにより、付着量が9.0~20g/m2のNiめっき層を形成するNiめっき工程と;
前記Niめっき工程後、670~760℃の温度範囲で、均熱時間5~180秒の熱処理を行って、前記Niめっき層の最表層のFe濃度Csを10~55質量%とする焼鈍・合金化処理工程と;
を有する
ことを特徴とするNi拡散めっき鋼板の製造方法。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020207029939A KR102428145B1 (ko) | 2018-04-13 | 2019-04-12 | Ni 확산 도금 강판 및 Ni 확산 도금 강판의 제조 방법 |
JP2020513463A JP6943335B2 (ja) | 2018-04-13 | 2019-04-12 | Ni拡散めっき鋼板及びNi拡散めっき鋼板の製造方法 |
CN201980024824.3A CN111989424B (zh) | 2018-04-13 | 2019-04-12 | Ni扩散镀层钢板以及Ni扩散镀层钢板的制造方法 |
US17/046,674 US20210032765A1 (en) | 2018-04-13 | 2019-04-12 | Ni DIFFUSION-PLATED STEEL SHEET AND METHOD FOR MANUFACTURING Ni DIFFUSION-PLATED STEEL SHEET |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018-077883 | 2018-04-13 | ||
JP2018077883 | 2018-04-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2019198819A1 true WO2019198819A1 (ja) | 2019-10-17 |
Family
ID=68164267
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2019/015978 WO2019198819A1 (ja) | 2018-04-13 | 2019-04-12 | Ni拡散めっき鋼板及びNi拡散めっき鋼板の製造方法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20210032765A1 (ja) |
JP (1) | JP6943335B2 (ja) |
KR (1) | KR102428145B1 (ja) |
CN (1) | CN111989424B (ja) |
WO (1) | WO2019198819A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022215642A1 (ja) * | 2021-04-09 | 2022-10-13 | 日本製鉄株式会社 | 表面処理鋼板 |
WO2023210822A1 (ja) * | 2022-04-29 | 2023-11-02 | 東洋鋼鈑株式会社 | 圧延表面処理鋼板の製造方法及び圧延表面処理鋼板 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114411213A (zh) * | 2022-02-17 | 2022-04-29 | 江苏东方九天新能源材料有限公司 | 一种锂电池用镀镍钢带的制备方法 |
CN114540604B (zh) * | 2022-02-23 | 2023-03-17 | 江苏东方九天新能源材料有限公司 | 一种电池容器用镀镍钢带及其制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014009401A (ja) * | 2012-07-03 | 2014-01-20 | Toyo Kohan Co Ltd | 電池容器用表面処理鋼板およびその製造方法、電池容器および電池 |
WO2016013575A1 (ja) * | 2014-07-22 | 2016-01-28 | 新日鐵住金株式会社 | 蓄電デバイス容器用鋼箔、蓄電デバイス用容器及び蓄電デバイス、並びに蓄電デバイス容器用鋼箔の製造方法 |
WO2017094920A1 (ja) * | 2015-12-03 | 2017-06-08 | 東洋鋼鈑株式会社 | 電池容器用表面処理鋼板 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09306438A (ja) * | 1996-05-17 | 1997-11-28 | Katayama Tokushu Kogyo Kk | 電池缶形成材料、該材料の製造方法、および該電池缶形成材料を用いて形成した電池缶 |
JP4555694B2 (ja) * | 2005-01-18 | 2010-10-06 | 新日本製鐵株式会社 | 加工性に優れる焼付け硬化型熱延鋼板およびその製造方法 |
SG176768A1 (en) * | 2009-06-09 | 2012-01-30 | Toyo Kohan Co Ltd | Nickel-plated steel sheet and process for producing battery can using the nickel-plated steel sheet |
TWI451005B (zh) * | 2011-04-07 | 2014-09-01 | Nippon Steel & Sumitomo Metal Corp | 容器用之含Ni表面處理鋼板及其製造方法 |
TWI489000B (zh) * | 2011-07-29 | 2015-06-21 | Nippon Steel & Sumitomo Metal Corp | An alloyed molten zinc plating layer and a steel sheet having the same, and a method for producing the same |
KR20130140496A (ko) * | 2012-06-14 | 2013-12-24 | 현대하이스코 주식회사 | 금속박 라미네이팅을 이용한 강 제품 제조 방법 및 이에 이용되는 핫 스탬핑용 소재 |
JP6023513B2 (ja) | 2012-08-29 | 2016-11-09 | 東洋鋼鈑株式会社 | 電池容器用表面処理鋼板、電池容器および電池 |
-
2019
- 2019-04-12 KR KR1020207029939A patent/KR102428145B1/ko active IP Right Grant
- 2019-04-12 US US17/046,674 patent/US20210032765A1/en active Pending
- 2019-04-12 CN CN201980024824.3A patent/CN111989424B/zh active Active
- 2019-04-12 WO PCT/JP2019/015978 patent/WO2019198819A1/ja active Application Filing
- 2019-04-12 JP JP2020513463A patent/JP6943335B2/ja active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014009401A (ja) * | 2012-07-03 | 2014-01-20 | Toyo Kohan Co Ltd | 電池容器用表面処理鋼板およびその製造方法、電池容器および電池 |
WO2016013575A1 (ja) * | 2014-07-22 | 2016-01-28 | 新日鐵住金株式会社 | 蓄電デバイス容器用鋼箔、蓄電デバイス用容器及び蓄電デバイス、並びに蓄電デバイス容器用鋼箔の製造方法 |
WO2017094920A1 (ja) * | 2015-12-03 | 2017-06-08 | 東洋鋼鈑株式会社 | 電池容器用表面処理鋼板 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022215642A1 (ja) * | 2021-04-09 | 2022-10-13 | 日本製鉄株式会社 | 表面処理鋼板 |
CN117120674A (zh) * | 2021-04-09 | 2023-11-24 | 日本制铁株式会社 | 表面处理钢板 |
JP7401840B2 (ja) | 2021-04-09 | 2023-12-20 | 日本製鉄株式会社 | 表面処理鋼板 |
WO2023210822A1 (ja) * | 2022-04-29 | 2023-11-02 | 東洋鋼鈑株式会社 | 圧延表面処理鋼板の製造方法及び圧延表面処理鋼板 |
Also Published As
Publication number | Publication date |
---|---|
CN111989424A (zh) | 2020-11-24 |
KR20200132975A (ko) | 2020-11-25 |
CN111989424B (zh) | 2024-04-23 |
US20210032765A1 (en) | 2021-02-04 |
JPWO2019198819A1 (ja) | 2021-02-12 |
JP6943335B2 (ja) | 2021-09-29 |
KR102428145B1 (ko) | 2022-08-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI609089B (zh) | High-strength cold-rolled steel sheet, high-strength hot dip galvanized steel sheet, and high-strength alloyed hot dip galvanized steel sheet | |
TWI390052B (zh) | 高強度罐用鋼板及其製造方法 | |
JP5983895B2 (ja) | 高強度鋼板およびその製造方法、ならびに高強度亜鉛めっき鋼板の製造方法 | |
WO2019198819A1 (ja) | Ni拡散めっき鋼板及びNi拡散めっき鋼板の製造方法 | |
EP2762602B1 (en) | Alloyed hot-dip galvanized steel sheet | |
JP6729821B2 (ja) | 表面処理鋼板および表面処理鋼板の製造方法 | |
EP3106528B1 (en) | High-strength hot-dip galvanized steel sheet, and method for manufacturing high-strength alloyed hot-dip galvanized steel sheet | |
KR20140102308A (ko) | 핫 스탬프 성형체 및 핫 스탬프 성형체의 제조 방법 | |
JP2007277652A (ja) | 加工性、パウダリング性、摺動性の良好な合金化溶融亜鉛メッキ鋼板の製造方法 | |
JP6729822B2 (ja) | 表面処理鋼板および表面処理鋼板の製造方法 | |
KR20190073469A (ko) | 고강도 강판 및 그 제조 방법 | |
JP2008019502A (ja) | 加工性、塗装焼付硬化性及び常温非時効性に優れた高強度亜鉛めっき鋼板並びにその製造方法 | |
EP2952603B1 (en) | High-strength hot-rolled steel sheet and method for manufacturing the same | |
JP2015081359A (ja) | 伸びの面内異方性が小さい高強度鋼板およびその製造方法 | |
TW201437389A (zh) | 高強度熱軋鋼板及其製造方法 | |
JP2006283070A (ja) | 加工性の良好な合金化溶融亜鉛メッキ鋼板の製造方法 | |
JP5397263B2 (ja) | 高張力冷延鋼板およびその製造方法 | |
JP6638874B1 (ja) | Ni拡散めっき鋼板及びNi拡散めっき鋼板の製造方法 | |
WO2018163871A1 (ja) | 高強度熱延めっき鋼板 | |
JP2001064750A (ja) | 曲げ性と深絞り性に優れた高強度冷延鋼板と高強度亜鉛めっき冷延鋼板およびその製造方法 | |
JP2013209728A (ja) | 耐時効性に優れた冷延鋼板およびその製造方法 | |
JPWO2021020439A1 (ja) | 高強度鋼板、高強度部材及びそれらの製造方法 | |
JP7151936B1 (ja) | 鋼板およびその製造方法 | |
JP5668361B2 (ja) | 高張力冷延鋼板およびその製造方法 | |
RU2575113C2 (ru) | Высокопрочный стальной лист - стальной лист и высокопрочный гальванизированный стальной лист, обладающие превосходной стабильностью формы, и способ их производства |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 19784375 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2020513463 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20207029939 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 19784375 Country of ref document: EP Kind code of ref document: A1 |