CN103649362A - Surface-treated steel plate, fuel pipe, cell can - Google Patents
Surface-treated steel plate, fuel pipe, cell can Download PDFInfo
- Publication number
- CN103649362A CN103649362A CN201280032782.6A CN201280032782A CN103649362A CN 103649362 A CN103649362 A CN 103649362A CN 201280032782 A CN201280032782 A CN 201280032782A CN 103649362 A CN103649362 A CN 103649362A
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- Prior art keywords
- steel plate
- treated steel
- alloy layer
- surface treated
- nickel alloy
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 83
- 239000010959 steel Substances 0.000 title claims abstract description 83
- 239000000446 fuel Substances 0.000 title claims abstract description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 92
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 57
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 40
- 238000007598 dipping method Methods 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 239000011780 sodium chloride Substances 0.000 claims description 20
- 238000010183 spectrum analysis Methods 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 7
- 238000005260 corrosion Methods 0.000 abstract description 45
- 230000007797 corrosion Effects 0.000 abstract description 45
- 229910000640 Fe alloy Inorganic materials 0.000 abstract 1
- 229910000990 Ni alloy Inorganic materials 0.000 abstract 1
- 239000000295 fuel oil Substances 0.000 abstract 1
- 238000000682 scanning probe acoustic microscopy Methods 0.000 abstract 1
- 229910052759 nickel Inorganic materials 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 23
- 239000011248 coating agent Substances 0.000 description 22
- 238000000576 coating method Methods 0.000 description 22
- 238000000137 annealing Methods 0.000 description 19
- 238000007669 thermal treatment Methods 0.000 description 17
- 230000003628 erosive effect Effects 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 230000002401 inhibitory effect Effects 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000000956 alloy Substances 0.000 description 9
- 230000002269 spontaneous effect Effects 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000007747 plating Methods 0.000 description 8
- 229910021607 Silver chloride Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910020816 Sn Pb Inorganic materials 0.000 description 4
- 229910020922 Sn-Pb Inorganic materials 0.000 description 4
- 229910008783 Sn—Pb Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 235000013361 beverage Nutrition 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910000655 Killed steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- -1 salt compound Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010731 rolling oil Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- 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
-
- 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
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (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)
Abstract
Provided is a surface-treated steel plate obtained by forming an iron-nickel alloy layer on the topmost surface, the surface-treated steel plate being characterized in that the Fe/Ni value obtained by Auger electron spectroscopy on the surface of the iron/nickel alloy layer is in the range of 0.3-2.0. In accordance with the present invention, there is provided a surface-treated steel plate having excellent corrosion resistance and in which the occurrence of pitting is effectively reduced when the surface-treated steel plate is exposed to various fuels such as automotive fuel oil.
Description
Technical field
The fuel tube and the battery case that the present invention relates to a kind of surface treated steel plate and use this surface treated steel plate to make.
Background technology
In the past, as the fuel tube material of automobile etc., main use be coated with Sn-Pb alloy steel plate, be coated with nickel and be coated with the multilayer plated steel sheet of Sn-Pb alloy.
Yet, because Sn-Pb alloy does not have erosion resistance to water, and the current potential of Sn-Pb alloy is higher than the current potential of Fe, therefore, can produce following problem: when carrying out melting plating, produce pin hole (Japanese: ピ ン ホ ー Le), under the effect of the corrosive deposits such as the moisture inevitably containing, by this pin hole, cause producing spot corrosion in Fuel Petroleum.
On the other hand, for example, in patent documentation 1, a kind of electroplating steel plate making as follows being disclosed: utilize to electroplate after surface of steel plate forms and makes composite deposite that fluorine cpd particle forms in being scattered in nickel coating, with the temperature more than fusing point of fluorine cpd particle, apply heat treated.
Patent documentation 1: Japanese kokai publication hei 8-232092 communique
Yet the inventor etc. are studied, found that the effect of the inhibiting point corrosion generation of above-mentioned patent documentation 1 disclosed plated steel sheet might not be enough.In addition, in above-mentioned patent documentation 1, owing to using fluorine cpd particle, therefore, from the viewpoint of environmental safety, consider also unsatisfactory.
Summary of the invention
The object of the present invention is to provide a kind of generation of effectively inhibiting point corrosion and there is the surface treated steel plate of excellent erosion resistance.In addition, the present invention also aims to provide a kind of fuel tube that uses such surface treated steel plate to make.
The inventor etc. have carried out conscientiously research to achieve these goals, found that and can utilize the surface treated steel plate that is formed with iron nickel alloy layer in outmost surface to realize above-mentioned purpose, the Fe/Ni value surperficial, that obtain through Auger electron spectrum analysis of this iron nickel alloy layer, in 0.3～2.0 scope, has completed the present invention thus.
That is, the invention provides a kind of surface treated steel plate, it is formed with iron nickel alloy layer in outmost surface and forms, and it is characterized in that, the Fe/Ni value obtaining through Auger electron spectrum analysis on the surface of above-mentioned iron nickel alloy layer is in 0.3～2.0 scope.
In surface treated steel plate of the present invention, preferably, the dipping current potential in sodium chloride aqueous solution of above-mentioned iron nickel alloy layer is with respect to the dipping current potential in sodium chloride aqueous solution of iron monomer in the scope in+0.05V～+ 0.25V.That is, " the dipping current potential of iron nickel alloy layer "-" the dipping current potential of iron monomer "=+ 0.05V～+ 0.25V.
In addition, adopt the present invention, can provide a kind of above-mentioned arbitrary surface treated steel plate is formed to the fuel tube processing.
And, adopt the present invention, can provide a kind of above-mentioned arbitrary surface treated steel plate is formed to the battery case processing.
Adopt the present invention, by forming iron nickel alloy layer in outmost surface, the Fe/Ni value surperficial, that obtain through Auger electron spectrum analysis of this iron nickel alloy layer in 0.3～2.0 scope, fuel tube and the battery case that the effectively generation of inhibiting point corrosion and the surface treated steel plate of excellent corrosion resistance can be provided and use such surface treated steel plate to make.
Accompanying drawing explanation
Fig. 1 is for the figure of the etch state of metal sheet is described.
Embodiment
Below, surface treated steel plate of the present invention is described.
The invention provides a kind of surface treated steel plate, it is formed with iron nickel alloy layer in outmost surface and forms, and it is characterized in that, the Fe/Ni value obtaining through Auger electron spectrum analysis on the surface of above-mentioned iron nickel alloy layer is in 0.3～2.0 scope.
steel plate
As the steel plate that becomes the substrate of surface treated steel plate of the present invention, as long as its excellent in workability, be not particularly limited, for example, can use by carbon aluminium-killed steel (carbon content 0.01 % by weight～0.15 % by weight), the carbon content ultra-low carbon steel below 0.003 % by weight or in ultra-low carbon steel, further add the steel plate that non-ageing ultra-low carbon steel that Ti, Nb form etc. forms.
In the present invention, the substrate using forms in the following manner: the hot-rolled sheet of above-mentioned steel is being carried out pickling and removing surperficial oxide skin (oxide film) afterwards, carrying out cold rollingly, then by ROLLING OIL electrolytic cleaning, afterwards, annealing, modified rolling prolong.Annealing in this situation can be continuous annealing or bell-type annealing (Japanese: any one box Ware Blunt), is not particularly limited.
iron nickel alloy layer
At surface treated steel plate of the present invention, in outmost surface, forming iron nickel alloy layer forms.The Fe/Ni value obtaining through Auger electron spectrum analysis on the surface of iron nickel alloy layer (mol ratio of Fe/Ni) is in 0.3～2.0 scope, preferably in 0.3～1.5 scope.
In the present invention, by the Fe/Ni value obtaining through Auger electron spectrum analysis on the surface of iron nickel alloy layer is controlled in above-mentioned scope, can effectively suppress to be exposed to the spot corrosion producing in the situation in the various fuel of fuel wet goods that automobile uses, thus, can make the excellent corrosion resistance of surface treated steel plate.
Herein, in the past, Nickeled Steel Plate was because erosion resistance was compared with high field of using pipe that the various fuel of fuel wet goods used at automobile uses, battery case etc. to require erosion resistance always, on the other hand, because nickel coating forms by plating, therefore there is the such problem of pin hole that produces.And there are the following problems: in Nickeled Steel Plate, produce the spot corrosion being caused by such pin hole, shortcoming, and the leakage that produces the contents such as fuel because of spot corrosion.
On the other hand, the discoveries such as the inventor are formed the Fe/Ni value obtaining through Auger electron spectrum analysis are controlled to the iron nickel alloy layer in above-mentioned scope by the surface at steel plate, can the generation of inhibiting point corrosion effectively when guaranteeing the excellent erosion resistance that nickel coating has, thus the present invention completed.Especially, the inventor etc. are dispersed in the nickel dam that erosion resistance is higher iron by trial, can the generation of inhibiting point corrosion effectively when guaranteeing the excellent erosion resistance of nickel coating thereby find.
If the Fe/Ni value obtaining through Auger electron spectrum analysis is too low, can not obtain the effect that inhibiting point corrosion produces, on the other hand, if Fe/Ni value is too high, can make the erosion resistance of iron nickel alloy layer reduce and cause the corrosion speed on the whole surface of alloy layer to be accelerated.The etch state of the metal sheets such as steel plate is described with reference to Fig. 1 herein.Fig. 1 (A) means the figure that produces corrosion metal sheet before, and Fig. 1 (B) means the figure of the metal sheet that has produced spot corrosion, and Fig. 1 (C) means the figure of the metal sheet that has produced general corrosion.In addition,, in Fig. 1 (A)～Fig. 1 (C), metal sheet contacts with corrosive liquid phase at accompanying drawing upside.In this case, except the situation that corrosive liquid directly contacts with metal sheet with liquid state, also comprise corrosive liquid gasification and gas that the situation that contacts with metal sheet with gaseous phase and corrosive liquid gasification form is separated out the situation of (Japanese: separate out) on metal sheet surface with the form of drop.As shown in Fig. 1 (B), spot corrosion is the local corrosion producing of thickness direction at metal sheet, and on the other hand, as shown in Fig. 1 (C), general corrosion is the corrosion producing on the whole surface of metal sheet, and general corrosion can make the thickness attenuation of metal sheet.That is,, in Fig. 1 (C), show the thickness of metal sheet from t
0reduce to t
1example.And, in the present invention, if Fe/Ni value is too low, can as shown in Fig. 1 (B), produce the such unfavorable condition of spot corrosion, on the other hand, if Fe/Ni value is too high, can make the progress of the general corrosion shown in Fig. 1 (C) accelerate, its result, can produce the such unfavorable condition of integral thickness attenuation.
In addition, in the present invention, the Fe/Ni value obtaining through Auger electron spectrum analysis, for example, can measure by the following method.That is, first, use sweep type Auger electron spectrum analytical equipment (AES) to measure the surface of iron nickel alloy layer, calculate the surperficial Ni of iron nickel alloy layer and the atom % of Fe.Then, use sweep type Auger electron spectrum analytical equipment to measure 5 positions in the surface of iron nickel alloy layer, and by the results averaged obtaining, can calculate thus Fe/Ni value (the atom % of the atom %/Ni of Fe).In addition, in the present invention, peak value using the peak value of the 820eV～850eV in the peak value that utilizes sweep type Auger electron spectrum analytical equipment to be measured as Ni, peak value using the peak value of 570eV～600eV as Fe, using the summation of above-mentioned Ni, Fe as 100 atom %, thus the atom % of mensuration Ni and Fe.
In addition, in surface treated steel plate of the present invention, the Fe/Ni value obtaining through Auger electron spectrum analysis of iron nickel alloy layer is in above-mentioned scope, in addition, preferably the dipping current potential of iron nickel alloy layer in sodium chloride aqueous solution is with respect to iron monomer in the scope of the dipping current potential in sodium chloride aqueous solution in+0.05V～+ 0.25V, in the scope of be more preferably in+0.07V～+ 0.22V.That is, preferably, in sodium chloride aqueous solution, the difference between the dipping current potential of iron nickel alloy layer and the dipping current potential of iron monomer is in above-mentioned scope.
In the present invention, by the Fe/Ni value obtaining through Auger electron spectrum analysis of iron nickel alloy layer is controlled in above-mentioned scope, in addition, the dipping current potential in sodium chloride aqueous solution of iron nickel alloy layer is all controlled in above-mentioned scope, can further improves the inhibition that spot corrosion is produced.If the dipping hypopotenia of iron nickel alloy layer (and the difference between the dipping current potential of iron monomer is too small), can make the erosion resistance of iron nickel alloy layer reduce and the corrosion speed on the whole surface of alloy layer is accelerated.On the other hand, if dipping current potential too high (and the difference between the dipping current potential of iron monomer is excessive) can make the inhibition that spot corrosion is produced reduce.
In addition, in the present invention, for the dipping current potential in sodium chloride aqueous solution of iron nickel alloy layer, for example, after can be in the sodium chloride aqueous solution that iron nickel alloy layer is immersed in to 5 % by weight, measure the spontaneous potential after 15 minutes, and using this spontaneous potential as dipping current potential.Herein, by iron nickel alloy layer be immersed in time in sodium chloride aqueous solution can according to the value of spontaneous potential after dipping reach stable till the needed time set, for example, can be set as described above 15 minutes.In addition, concrete measuring method as dipping current potential, make electrolytic solution be 5 % by weight sodium chloride aqueous solution, to make reference electrode be Ag/AgCl, make electrode is Pt, make to measure temperature is to measure under the condition of 35 ℃, thus, measure iron nickel alloy layer with respect to the spontaneous potential of Ag/AgCl, obtain poor with respect between the spontaneous potential of Ag/AgCl of the spontaneous potential of acquisition and Fe monomer, thereby can measure the dipping current potential in sodium chloride aqueous solution of iron nickel alloy layer.
In addition, in the present invention, dipping current potential and potential difference iron monomer dipping current potential in sodium chloride aqueous solution between of iron nickel alloy layer in sodium chloride aqueous solution is to calculate by " the dipping current potential of iron nickel alloy layer "-" the dipping current potential of iron monomer ".
In the present invention, the method as forming iron nickel alloy layer, is not particularly limited, and for example, can list following method.That is, can list following methods etc.: use nickel plating bath to form nickel coating on the surface of steel plate, then, by it being applied to thermal treatment, make its thermodiffusion, thereby form iron nickel alloy layer.But in the present invention, the method as forming iron nickel alloy layer, is not particularly limited as aforesaid method.
Particularly, first, as nickel plating bath, use the plating bath of conventionally using when nickel plating, the acid bath of ス Le Off ァ ミ Application), lemon acid bath (Japanese:, forming thickness is that 0.3 μ m～5 μ m, preferred thickness are the nickel coating of 0.3 μ m～2 μ m the acid bath of Network エ Application), boron fluoride bathes (Japanese: ほ う Off ッ compound is bathed) and muriate is bathed (Japanese: salt compound is bathed) etc. watt is bathed, thionamic acid bathes (Japanese:.For example, nickel coating can be bathed and be consisted of the single nickel salt of 200g/L～350g/L, the plating bath of the nickelous chloride of 20g/L～50g/L, 20g/L～50g/L boric acid is bathed as watt by use, at pH3～pH4.8, bath temperature 40 ℃～70 ℃, current density 5A/dm
2～30A/dm
2condition under form.If the thickness of nickel coating is excessively thin, can make the alloy layer attenuation forming in subsequent handling, thereby likely make the erosion resistance on the whole surface of alloy layer reduce, on the other hand, if the thickness of nickel coating is blocked up,, in the heat treatment process of subsequent handling, likely can not make iron fully spread and cannot form alloy, in addition, also can cause cost to rise.
Then, for the steel plate that is formed with nickel coating, by it being applied to thermal treatment, make its thermodiffusion, thereby form iron nickel alloy layer (iron-nickel diffusion layer).Thermal treatment now can be any one annealing in continuous annealing or bell-type annealing, and in addition, heat-treat condition, as long as suitably select accordingly with the thickness of nickel coating, for example, when utilizing bell-type annealing to heat-treat, preferably adopts following condition.
Thermal treatment temp: 400 ℃～800 ℃
Heat treatment time: 30 minutes～16 hours
Heat-treating atmosphere: non-oxidizing atmosphere or restitutive protection's gas atmosphere
In addition, when thermal treatment is continuous annealing, preferably adopt following condition.
Thermal treatment temp: 600 ℃～900 ℃
Heat treatment time: 3 seconds～120 seconds
Heat-treating atmosphere: non-oxidizing atmosphere or restitutive protection's gas atmosphere
In addition, no matter in any annealing in bell-type annealing, continuous annealing, when the thinner thickness of nickel coating, all preferably make thermal treatment temp in above-mentioned condition lower and make heat treatment time shorter.In addition, when the thickness of nickel coating is thicker, all preferably make thermal treatment temp in above-mentioned condition higher and make heat treatment time longer.In addition; when making heat-treating atmosphere be restitutive protection's gas atmosphere; ア Application モ ニ ア Network ラ ッ Network method) and the shielding gas generating, contain 75% hydrogen-25% hydrogen as shielding gas, preferably use and utilize heat to transmit the good rich hydrogen annealing (the Japanese: (Japanese: of ammonia cracking process water element enrichment Ware Blunt) that is called as.
If thermal treatment temp is too low or heat treatment time is too short, can make the thermodiffusion in iron nickel alloy layer insufficient, the Fe/Ni value step-down on the iron nickel alloy layer surface obtaining through Auger electron spectrum analysis, result, can not obtain the effect that inhibiting point corrosion produces.On the other hand, if thermal treatment temp is too high or heat treatment time is long, can make the Fe/Ni value on the iron nickel alloy layer surface that obtain through Auger electron spectrum analysis become too high, make the erosion resistance of iron nickel alloy layer reduce and the corrosion speed on the whole surface of alloy layer is accelerated.
As mentioned above, by form the iron nickel alloy layer of afore mentioned rules on steel plate, can obtain surface treated steel plate of the present invention.Surface treated steel plate of the present invention is in being exposed to corrosive liquid content, steam in the situation that, for example be exposed in the situation in the various fuel of fuel wet goods that automobile uses, be exposed in the situation in the electrolytic solution of battery, effectively the generation of inhibiting point corrosion and excellent corrosion resistance.Therefore, surface treated steel plate of the present invention can be applicable to be exposed to the state in the liquid content such as various fuel and the purposes used.Particularly, can be applicable to the various uses such as fuel tube, fuel container and battery case.Or, even when surface treated steel plate of the present invention is applied to beverages can, food cans purposes, compare with the material that was applied to beverages can, food cans purposes in the past, also can bring into play excellent erosion resistance, therefore, surface treated steel plate of the present invention also can be applicable to beverages can, food cans purposes.Especially, due to form the iron nickel alloy layer of surface treated steel plate of the present invention be iron and nickel all fully alloying form, therefore,, even when surface treated steel plate of the present invention is applied to above-mentioned beverages can, food cans purposes, also can suitably suppress the stripping of iron or nickel.
fuel tube
Fuel tube of the present invention can make by the surface treated steel plate of the invention described above being formed to processing.Particularly, fuel tube of the present invention can make by the following method: utilize levelling arm to carry out shape correction to the surface treated steel plate of the invention described above, utilize after cutting machine (slitter) cuts into the outside dimension of regulation, utilize forming mill that surface treated steel plate is configured as to tubulose with iron nickel alloy aspect to the mode of inner surface side, utilize HFI welding that the end face of long side direction is stitched to weldering each other.Because the fuel tube of the present invention so making is to use the surface treated steel plate of the invention described above to make, therefore, in the time of in being exposed to the various fuel of fuel wet goods that automobile uses, the effectively generation of inhibiting point corrosion and excellent corrosion resistance.Therefore, fuel tube of the present invention can be applicable to following various uses, such as for fuel being imported to the oil feed pipe of case, in case, fuel is imported to the pipe of engine and the pipe of ventilating etc.In addition, as the fuel in this situation, can list the various fuel that the automobiles such as gasoline, light oil, bio-ethanol (bioethanol) or biodiesel fuel are used.
battery case
Battery case of the present invention is to use the surface treated steel plate of the invention described above to make.Particularly, battery case of the present invention be by the surface treated steel plate to the invention described above stretch, attenuate utilize DI or DTR is shaped so that iron nickel alloy layer is positioned at the mode of battery case inner surface side forms and make.Because the battery case of the present invention so making is to utilize the surface treated steel plate of the invention described above to make, therefore, the effectively generation of inhibiting point corrosion and excellent corrosion resistance.Especially, the surface treated steel plate of the invention described above is not only in the situation that be exposed to the various fuel of fuel wet goods that automobile is used, even in the situation that use in the mode contacting with alkaline electrolytic solution, the also effectively generation of inhibiting point corrosion and can realize excellent erosion resistance.Therefore, battery case of the present invention can be applicable to use as alkaline cell, nickel metal hydride battery etc. the cell container of the battery of alkaline electrolytic solution.
Below, enumerate embodiment and be described more specifically the present invention, but the present invention is not limited to above-described embodiment.
In addition, the definition of each characteristic and evaluation method are as described below.
fe/Ni value
Effects on surface is processed the top layer of the iron nickel alloy layer of steel plate and is carried out the etching of about 10nm, the atom % that Ni and Fe are measured in 5 positions of the surface treated steel plate of use sweep type Auger electron spectrum analytical equipment (AES) after etching, has obtained the Fe/Ni value obtaining through Auger electron spectrum analysis thus.
dipping current potential
Will be to retain
the mode in the region surface treated steel plate that carried out covering after processing be immersed in the sodium chloride aqueous solution of 5 % by weight, at reference electrode, be Ag/AgCl, to electrode, be Pt, to measure temperature be under the condition of 35 ℃, to measure the spontaneous potential with respect to Ag/AgCl of iron nickel alloy layer, and obtain poor with respect between the spontaneous potential of Ag/AgCl of the spontaneous potential of acquisition and Fe monomer, measured thus the dipping current potential in sodium chloride aqueous solution of iron nickel alloy layer.
spot corrosion
The surface treated steel plate that the mode in the region with reservation 20mm * 20mm has been carried out covering after processing is immersed in the sodium chloride aqueous solution of 5 % by weight, at reference electrode, be Ag/AgCl, to electrode, be Pt, to measure temperature be under the condition of 35 ℃, to apply gradually forcibly current potential to carry out anodic polarization, and keep 30 minutes under the current potential of corrosion zero hour of surface treated steel plate, thereby promoted corrosion.And, after having promoted corrosion, utilize visual identification effects on surface process steel plate whether in the region generating of 20mm * 20mm spot corrosion observe.
embodiment 1
As matrix, prepared the cold-reduced sheet (thickness 0.25mm) with the carbon aluminium-killed steel of the chemical constitution shown in following to anneal and the steel plate that makes.
C:0.045 % by weight, Mn:0.23 % by weight, Si:0.02 % by weight, P:0.012 % by weight, S:0.009 % by weight, Al:0.063 % by weight, N:0.0036 % by weight, remainder: Fe and inevitable impurity
Then, ready steel plate has been carried out to the pickling that alkaline electrolysis degreasing, sulfuric acid flood, with following condition, carried out nickel plating afterwards, thereby formed the nickel coating of thickness 0.5 μ m.
Bathe and form: single nickel salt 250g/L, nickelous chloride 45g/L, boric acid 30g/L
pH：3～4.8
Bathe temperature: 60 ℃
Current density: 10A/dm
2
Then, utilize bell-type annealing, under the condition of 650 ℃ of temperature, non-oxidizing atmosphere (vacuum annealing), to being formed with the steel plate of nickel coating, carry out the thermal treatment of two hours, by nickel coating is carried out to heat diffusion treatment, thereby form iron nickel alloy layer, made surface treated steel plate.For the surface treated steel plate so making, according to aforesaid method to the dipping current potential in sodium chloride aqueous solution of the Fe/Ni value obtaining through Auger electron spectrum analysis, iron nickel alloy layer, have or not and produce spot corrosion and evaluate respectively.The results are shown in table 1.
embodiment 2
Except heat treatment time is changed into 4 hours, in the mode identical with embodiment 1, made surface treated steel plate and similarly evaluated.The results are shown in table 1.
Embodiment 3
Except making the thickness of nickel coating, be 1 μ m, in the mode identical with embodiment 2, made surface treated steel plate and similarly evaluated.The results are shown in table 1.
embodiment 4
Except heat treatment time is changed into 8 hours, in the mode identical with embodiment 1, made surface treated steel plate and similarly evaluated.The results are shown in table 1.
Except heat treatment time is changed into 8 hours, in the mode identical with embodiment 3, made surface treated steel plate and similarly evaluated.The results are shown in table 1.
embodiment 6
Except make the thickness of nickel coating be 2 μ m and heat treatment time is changed into 12 hours, in the mode identical with embodiment 1, made surface treated steel plate similarly evaluating.The results are shown in table 1.
embodiment 7
Except thermal treatment being changed into 800 ℃ of temperature, 1 minute, the continuous annealing of non-oxidizing atmosphere (vacuum annealing), in the mode identical with embodiment 1, made surface treated steel plate and similarly evaluated.The results are shown in table 1.
embodiment 8
Except thermal treatment temp being changed into 900 ℃, in the mode identical with embodiment 7, made surface treated steel plate and similarly evaluated.The results are shown in table 1.
comparative example 1
Except not heat-treating, in the mode identical with embodiment 1, made surface treated steel plate and similarly evaluated.The results are shown in table 1.
comparative example 2～comparative example 4
Except making the thickness of nickel coating be respectively 1 μ m(comparative example 2), 2 μ m(comparative examples 3), 3 μ m(comparative examples 4), in the mode identical with comparative example 1, made surface treated steel plate similarly evaluating.The results are shown in table 1.
comparative example 5
Except making the thickness of nickel coating, be 1 μ m, in the mode identical with embodiment 1, made surface treated steel plate and similarly evaluated.The results are shown in table 1.
comparative example 6
Except making the thickness of nickel coating, be 3 μ m, in the mode identical with embodiment 1, made surface treated steel plate and similarly evaluated.The results are shown in table 1.
comparative example 7,8
Except heat treatment time is respectively 4 hours (comparative example 7), 8 hours (comparative example 8), in the mode identical with comparative example 6, made surface treated steel plate and similarly evaluated.The results are shown in table 1.
comparative example 9
Except thermal treatment temp being changed into 720 ℃, in the mode identical with embodiment 7, made surface treated steel plate and similarly evaluated.The results are shown in table 1.
comparative example 10
Except thermal treatment being changed into 720 ℃ of temperature, 1 minute, the continuous annealing of non-oxidizing atmosphere (vacuum annealing), in the mode identical with embodiment 3, made surface treated steel plate and similarly evaluated.The results are shown in table 1.
comparative example 11
Except thermal treatment temp being changed into 800 ℃, in the mode identical with comparative example 10, made surface treated steel plate and similarly evaluated.The results are shown in table 1.
comparative example 12
Except thermal treatment temp being changed into 900 ℃, in the mode identical with comparative example 10, made surface treated steel plate and similarly evaluated.The results are shown in table 1.
table 1
As shown in table 1, in the embodiment 1～embodiment 8 of the Fe/Ni value obtaining through Auger electron spectrum analysis on the surface of iron nickel alloy layer in 0.3～2.0 scope, suppress the generation of spot corrosion and obtained good result, in addition, in embodiment 1～embodiment 8, in sodium chloride aqueous solution, with respect in the dipping current potential of the iron monomer also scope in+0.05V～+ 0.25V.
On the other hand, in outmost surface, be formed with nickel coating and do not form the Fe/Ni value obtaining through Auger electron spectrum analysis on the comparative example 1～comparative example 4 of iron nickel alloy layer and the surface of iron nickel alloy layer and be less than in comparative example 5～comparative example 12 of 0.3, produced spot corrosion, therefore, in the situation that surface treated steel plate is applied to fuel tube, battery case purposes etc., with the state being exposed in corrosive liquid content, use, content likely leaks to outside via the hole producing because of spot corrosion.
Claims (4)
1. a surface treated steel plate, it is formed with iron nickel alloy layer in outmost surface and forms, it is characterized in that,
The Fe/Ni value obtaining through Auger electron spectrum analysis on the surface of above-mentioned iron nickel alloy layer is in 0.3～2.0 scope.
2. surface treated steel plate according to claim 1, is characterized in that,
The dipping current potential in sodium chloride aqueous solution of above-mentioned iron nickel alloy layer is with respect to the dipping current potential in sodium chloride aqueous solution of iron monomer in the scope in+0.05V～+ 0.25V.
3. a fuel tube, wherein,
This fuel tube is by the surface treated steel plate to described in claim 1 or 2, to form processing to form.
4. a battery case, wherein,
This battery case is by the surface treated steel plate to described in claim 1 or 2, to form processing to form.
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| CN201610921123.8A CN107012488B (en) | 2011-06-30 | 2012-06-29 | Surface treated steel plate, cartridge and battery case |
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| JP2011145263 | 2011-06-30 | ||
| JP2011-145263 | 2011-06-30 | ||
| PCT/JP2012/066641 WO2013002356A1 (en) | 2011-06-30 | 2012-06-29 | Surface-treated steel plate, fuel pipe, cell can |
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| WO2010143374A1 (en) * | 2009-06-09 | 2010-12-16 | 東洋鋼鈑株式会社 | Nickel-plated steel sheet and process for producing battery can using the nickel-plated steel sheet |
| WO2011033774A1 (en) * | 2009-09-18 | 2011-03-24 | 東洋鋼鈑株式会社 | Steel sheet used to manufacture pipe and having corrosion-resistant properties against fuel vapors, and pipe and fuel supply pipe that use same |
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| CN1082988A (en) * | 1992-06-22 | 1994-03-02 | 东洋钢钣株式会社 | Erosion-resisting Nickeled Steel Plate or steel bar and method for making thereof |
| CN1170782A (en) * | 1996-05-21 | 1998-01-21 | 片山特殊工业株式会社 | Battery shell forming material, battery shell forming method and battery shell |
| JP3745626B2 (en) * | 2001-01-09 | 2006-02-15 | 新日本製鐵株式会社 | Ni-plated steel plate for alkaline manganese battery positive electrode can |
| WO2010143374A1 (en) * | 2009-06-09 | 2010-12-16 | 東洋鋼鈑株式会社 | Nickel-plated steel sheet and process for producing battery can using the nickel-plated steel sheet |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP6162601B2 (en) | 2017-07-12 |
| JPWO2013002356A1 (en) | 2015-02-23 |
| JP6400140B2 (en) | 2018-10-03 |
| CN107012488B (en) | 2019-03-08 |
| JP2017122281A (en) | 2017-07-13 |
| CN107012488A (en) | 2017-08-04 |
| IN2014CN00464A (en) | 2015-04-03 |
| KR20140053138A (en) | 2014-05-07 |
| WO2013002356A1 (en) | 2013-01-03 |
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