WO2014157104A1 - ろう付け性に優れたフェライト系ステンレス鋼板、熱交換器、熱交換器用フェライト系ステンレス鋼板、フェライト系ステンレス鋼、燃料供給系部材用フェライト系ステンレス鋼、及び燃料供給系部品 - Google Patents
ろう付け性に優れたフェライト系ステンレス鋼板、熱交換器、熱交換器用フェライト系ステンレス鋼板、フェライト系ステンレス鋼、燃料供給系部材用フェライト系ステンレス鋼、及び燃料供給系部品 Download PDFInfo
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- WO2014157104A1 WO2014157104A1 PCT/JP2014/058112 JP2014058112W WO2014157104A1 WO 2014157104 A1 WO2014157104 A1 WO 2014157104A1 JP 2014058112 W JP2014058112 W JP 2014058112W WO 2014157104 A1 WO2014157104 A1 WO 2014157104A1
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- stainless steel
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- brazing
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- 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
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
- B23K1/0012—Brazing of heat exchangers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/19—Soldering, e.g. brazing, or unsoldering taking account of the properties of the materials to be soldered
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- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/002—Heat treatment of ferrous alloys containing Cr
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- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
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- 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
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
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- C—CHEMISTRY; METALLURGY
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
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- C—CHEMISTRY; METALLURGY
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/30—Ferrous alloys, e.g. steel alloys containing chromium with cobalt
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- 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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
- C23G1/086—Iron or steel solutions containing HF
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/19—Iron or steel
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/28—Cleaning or pickling metallic material with solutions or molten salts with molten salts
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
- C25F1/02—Pickling; Descaling
- C25F1/04—Pickling; Descaling in solution
- C25F1/06—Iron or steel
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
- F28F21/081—Heat exchange elements made from metals or metal alloys
- F28F21/082—Heat exchange elements made from metals or metal alloys from steel or ferrous alloys
- F28F21/083—Heat exchange elements made from metals or metal alloys from steel or ferrous alloys from stainless steel
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- 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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/005—Ferrite
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- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
- F02M2200/00—Details of fuel-injection apparatus, not otherwise provided for
- F02M2200/05—Fuel-injection apparatus having means for preventing corrosion
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
- F02M2200/00—Details of fuel-injection apparatus, not otherwise provided for
- F02M2200/90—Selection of particular materials
- F02M2200/9053—Metals
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D21/00—Heat-exchange apparatus not covered by any of the groups F28D1/00 - F28D20/00
- F28D21/0001—Recuperative heat exchangers
- F28D21/0003—Recuperative heat exchangers the heat being recuperated from exhaust gases
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F2275/00—Fastening; Joining
- F28F2275/04—Fastening; Joining by brazing
Definitions
- the present invention relates to a ferritic stainless steel plate used as a material for members assembled by brazing, and a heat exchanger and a fuel supply system component using the same.
- exhaust gas regulations have been strengthened due to increasing awareness of environmental issues, and efforts are being made to reduce carbon dioxide emissions.
- fuel-related efforts such as bioethanol and biodiesel fuel
- EGR exhaust Gas Recirculation
- DPF Diesel Particulate Filter
- urea SCR Selective Catalytic
- the exhaust heat recovery unit is a system that heats engine cooling water with exhaust gas and uses it to warm up the heater and the engine, and is also called an exhaust heat recirculation system.
- Such a heat exchanger is required to have good thermal efficiency and good thermal conductivity, and to have excellent corrosion resistance against exhaust gas condensed water because it contacts exhaust gas.
- EGR coolers and exhaust heat recovery devices that may lead to a serious accident such as leakage of cooling water are required to have higher safety and better corrosion resistance.
- the structure of the heat exchange part is complicated, it may be assembled by welding joint, but may be assembled by brazing joint. The material of the heat exchange part assembled by brazing and joining needs to have good brazing properties.
- austenitic stainless steels such as SUS304 and SUS316L are used as materials for heat exchangers, but ferritic stainless steels are attracting attention from the viewpoint of intergranular corrosion resistance and stress corrosion cracking resistance in addition to thermal conductivity. ing.
- Patent Document 1 includes brazing filler material including C: 0.01% or less, Cr: 10.5 to 13.5%, N: 0.05% or less, and at least one of Ti, Nb, and Ta.
- Ferritic stainless steel is disclosed which is characterized by being wetted by
- the amount of Ti is regulated to 0.12% or less because it affects the wettability, and from the viewpoint of brazing, it is desirable that no additive be added.
- Patent Document 2 C: 0.03% or less, Si: 0.02-1.5%, Mn: 0.02-2%, Cr: 10-22%, Nb: 0.03-1%, A ferritic stainless steel excellent in brazeability containing Al: 0.5% or less and N: 0.05% or less is disclosed.
- brazing properties are secured by limiting the amounts of Ti and Al from the relational expression of Ti, N, and Al.
- Patent Document 3 C: 0.03% or less, Si: more than 0.1% and 1% or less, Mn: 2% or less, P: 0.05% or less, S: 0.03% or less, Cr: Ferritic stainless steel for brazing containing 16 to 25%, Nb: 0.15 to 0.8%, Ti: 0.03% or less, Al: 0.03% or less, N: 0.03% or less It is disclosed.
- brazing properties are ensured particularly in a hydrogen atmosphere by further strictly limiting the amount of Al added to Ti.
- the fuel discharged from the fuel tank is pressurized by a pump and supplied to the engine through a delivery pipe or the like. Since the pressurized fuel is intermittently injected into the engine, the fuel pressure tends to fluctuate. For this reason, pressure adjusting parts may be required. Since the fuel supply system parts such as the pressure adjusting parts are arranged close to the engine, the temperature is likely to rise. Therefore, the material material used for the fuel supply system parts is required to have strength. In order to ensure the strength, it is conceivable to increase the thickness of the material. However, increasing the thickness of the material increases the weight, which causes an increase in fuel consumption.
- biofuels such as bioethanol and biodiesel
- biodiesel is expanding from the viewpoint of suppressing carbon dioxide emissions.
- bioethanol contained in biofuel is a factor that corrodes aluminum. Therefore, the material used for the fuel supply system parts needs to have good corrosion resistance against biofuel.
- stainless steel has attracted attention as a material for fuel supply system parts.
- fuel supply system parts such as delivery pipes have complicated structures. For this reason, it is often assembled by brazing and joining. Therefore, the material used for the fuel supply system parts needs to have not only good strength and corrosion resistance but also good brazing properties.
- Patent Document 4 discloses a fuel supply device capable of attenuating the fuel pressure pulsation of a delivery pipe from a low fuel pressure to a high fuel pressure. Patent Document 4 discloses that stainless steel can be used for the pulsation damping pipe. However, details of the used stainless steel material are not described.
- Patent Document 5 discloses a high-pressure fuel delivery pipe for a direct-injection engine that eliminates leakage of high-pressure fuel from the joint surface between the mounting stay and the main body pipe and increases the coupling strength of the mounting stay. It is described that this delivery pipe is manufactured by brazing stainless steel. However, Patent Document 5 does not describe details of the stainless steel used.
- Patent Document 6 in mass%, C: ⁇ 0.01%, Si: ⁇ 1.0%, Mn: ⁇ 1.5%, P: ⁇ 0.06%, S: ⁇ 0.03%, Cr: 11 to 23%, Ni: ⁇ 2.0%, Mo: 0.5 to 3.0%, Al: ⁇ 1.0%, N: ⁇ 0.04%, Cr + 3.3Mo ⁇ 18 Satisfying the relational expression, satisfying the relational expression of Nb: ⁇ 0.8%, Ti: ⁇ 1.0%, 18 ⁇ Nb / (C + N) + 2Ti / (C + N) ⁇ 60 A ferritic stainless steel sheet containing a ferrite crystal grain number of 6.0 or more and an average r value of 2.0 or more is disclosed.
- Patent Document 7 in mass%, C: ⁇ 0.01%, Si: ⁇ 1.0%, Mn: ⁇ 1.5%, P: ⁇ 0.06%, S: ⁇ 0.03%, Al: ⁇ 1.0%, Cr: 11-20%, Ni: ⁇ 2.0%, Mo: 0.5-3.0%, V: 0.02-1.0%, N: ⁇ 0. Steel plate that contains 04%, Nb: 0.01 to 0.8%, Ti: 0.01 to 1.0%, or one or two, and is deformed by 25% by uniaxial tension A ferritic stainless steel sheet having a surface waviness height of 50 ⁇ m or less is disclosed. Both Patent Document 6 and Patent Document 7 deal with corrosion resistance against ordinary gasoline and do not describe biofuel.
- Materials used for automobile fuel supply system parts are mainly required to have strength, corrosion resistance and brazing.
- Stainless steel expresses corrosion resistance by forming a passive film rich in Cr on the surface, and a higher protective film is formed as a material having a higher Cr content, and exhibits excellent corrosion resistance.
- Stainless steel when the stainless steel is brazed, it is necessary to reduce and remove the passive film once.
- the reduction characteristics of a passive film formed on stainless steel, particularly high Cr stainless steel have not been considered.
- Stainless steel with a high Cr content has a high reduction resistance of the passive film.
- stainless steel that has both corrosion resistance and brazing has not been proposed.
- the present invention has been proposed in view of such conventional circumstances.
- the first object of the present invention is to provide a ferritic stainless steel sheet having excellent brazing properties that can be suitably used as a material for members assembled by brazing and joining such as heat exchangers.
- a second object of the present invention is to provide a ferritic stainless steel sheet that can be suitably used as a material for a member assembled by brazing and joining such as a fuel supply system member and has excellent brazeability.
- a second object of the present invention is to provide a ferritic stainless steel for a fuel supply system member and a fuel supply system component that have both corrosion resistance and brazing properties and are excellent in strength.
- the gist of the first aspect of the present invention aimed at solving the first problem is as follows. [1] By mass%, C: 0.03% or less, N: 0.05% or less, Si: 1% or less, Mn: 1.2% or less, Cr: 14% or more and 28% or less, Nb: 8 ( C + N) and not more than 0.8%, and Al: not more than 0.1%, the balance being Fe and inevitable impurities, and a film satisfying Formula 1 is formed on the surface Ferritic stainless steel sheet with excellent properties.
- Equation 1 d f ⁇ Cr f +5 (Si f + 3Al f ) ⁇ 2.0 (Formula 1)
- d f is a unit that indicates the thickness of nm of the coating
- Cr f represents the Cr cations fraction in the film
- Si f represents the Si cation fraction in the film
- Al f is in the film
- the Al cation fraction is shown.
- a heat exchanger comprising a heat exchange part made of a brazed member, wherein the member is made of the ferritic stainless steel plate according to any one of [1] to [3].
- Equation 1 d f ⁇ Cr f +5 (Si f + 3Al f ) ⁇ 2.0 (Formula 1)
- d f is a unit that indicates the thickness of nm of the coating
- Cr f represents the Cr cations fraction in the film
- Si f represents the Si cation fraction in the film
- Al f is in the film
- the Al cation fraction is shown.
- the gist of the second aspect of the present invention aimed at solving the second problem is as follows. [8] By mass%, C: 0.03% or less, N: 0.05% or less, Si: 1% or less, Mn: 1.2% or less, Cr: 15% or more and 23% or less, Nb: 8 ( C + N) + 0.1% or more and 0.8% or less, and Al: 0.1% or less, the balance is Fe and inevitable impurities, and a film satisfying Formula 2 and Formula 3 is formed on the surface.
- Ferritic stainless steel characterized by that.
- Equation 2 d f ⁇ Cr f +5 (Si f + 3Al f ) ⁇ 2.0 (Formula 2) 0.18 ⁇ Cr f ⁇ 0.5 (Formula 3)
- d f is a unit that indicates the thickness of nm of the film
- Si f denotes the Si cation fraction in the film
- Al f denotes the Al cation fraction in the film.
- Cr f denotes the Cr cations fraction in the film.
- Stainless steel [10] Further, in mass%, V: 0.5% or less, W: 1% or less, B: 0.005% or less, Zr: 0.5% or less, Sn: 0.5% or less, Co: 0 .2% or less, Mg: 0.002% or less, Ca: 0.002% or less, REM: 0.01% or less, Sb: 0.5% or less, Ta: 0.5% or less, and Ga: 0.
- a fuel supply system component comprising a brazed member, wherein the member is made of the ferritic stainless steel according to any one of [8] to [10].
- Equation 2 d f ⁇ Cr f +5 (Si f + 3Al f ) ⁇ 2.0 (Formula 2) 0.18 ⁇ Cr f ⁇ 0.5 (Formula 3)
- d f is a unit that indicates the thickness of nm of the film
- Si f denotes the Si cation fraction in the film
- Al f denotes the Al cation fraction in the film.
- Cr f denotes the Cr cations fraction in the film.
- the ferritic stainless steel sheet according to the first aspect can be suitably used for automobile parts such as EGR coolers, oil coolers, exhaust heat recovery devices, and fuel delivery parts.
- the ferritic stainless steel plate according to the first aspect is a heat exchanger related to hot water supply, for gas, to a secondary heat exchanger of a latent heat recovery type water heater, and for electricity, an Ecocute (registered trademark) plate type heat exchanger. It can be used suitably for a vessel.
- the ferritic stainless steel plate according to the first aspect can be suitably used for members of heat exchangers of various plants assembled by other brazing joints.
- the ferritic stainless steel according to the second aspect of the present invention, the ferritic stainless steel for fuel supply system members, and the fuel supply system parts are excellent in brazeability, excellent in corrosion resistance in biofuel, and more excellent. Has strength.
- the present embodiment is directed to a ferritic stainless steel sheet used as a material for a member to be brazed using Ni brazing or Cu brazing. Brazing is performed at 950 to 1200 ° C. in a vacuum or in a hydrogen atmosphere. At this time, argon gas, nitrogen gas, or the like may be used in combination for atmosphere control or replacement. In brazing, the base material (raw material) is wetted to fill the gap, thereby joining the base material. When an oxide film is present on the surface of the material, it becomes difficult to wet and brazeability is hindered.
- a Cr-rich (Fe, Cr) oxide film is formed, thereby exhibiting excellent corrosion resistance. In order to ensure wettability, it is necessary to remove this film.
- brazing is performed under conditions of a vacuum degree or a low dew point. Specifically, the brazing of the stainless steel plate is performed under a condition lower than the vacuum level or dew point at which Cr and Cr 2 O 3 are balanced at the brazing temperature. When brazing a stainless steel plate, the stainless steel is usually kept at the brazing temperature for about 10 to 30 minutes. How can the film formed on the surface of the stainless steel plate be reduced within this finite time? However, it will have a great influence on the brazability.
- (Formula 1) is based on the following matters.
- the Cr cation fraction in the (Fe, Cr) oxide film formed on the surface is higher for stainless steel plates with higher Cr content, and is affected by the manufacturing conditions of the material before brazing, such as annealing and pickling. Also receive.
- the thickness of the oxide film becomes thinner as the stainless steel plate having a higher Cr content, and is also affected by the material manufacturing conditions. Therefore, it is necessary to secure the brazing property by suppressing the growth of the film and reducing the film thickness for the stainless steel plate having a higher Cr content.
- Si is contained in stainless steel sheets in an amount of 1% or less, but Si may be concentrated in the film during the finish annealing and pickling processes, and may remain in the film as Si oxide to deteriorate the brazeability. There is. The reason why the Si oxide is concentrated in the film in the finish annealing and pickling processes is not clear, but at present, it is considered as follows.
- Fe-rich (Fe, Cr) oxide is generated in the outer layer and Cr-rich (Fe, Cr) oxide is generated in the inner layer.
- Si can exist as an oxide inside the Cr-rich (Fe, Cr) oxide. Si oxides are more likely to be generated as Cr-rich (Fe, Cr) oxides become more stable. For this reason, as a base material factor, it is guessed that a stainless steel plate with much Cr content tends to produce Si oxide. As a manufacturing process factor, it is presumed that the higher the annealing temperature and the longer the annealing time, the easier it is to produce Si oxide.
- the main purpose of the pickling process following the finish annealing is to dissolve and remove the (Fe, Cr) oxide generated by annealing, but at the same time, a part of the base material is also dissolved. Since the Si oxide is stable in a neutral to acidic region, it is effective to remove the Si oxide as the base material is dissolved or to treat the steel in an alkali capable of dissolving the Si oxide. In order to dissolve and remove the Si oxide together with the base material by pickling, it is conceivable to increase the temperature and concentration of the pickling solution and to increase the pickling time. In order to dissolve Si oxide in alkali, for example, the salt method (method of heating a commercially available descaling alkali salt mainly composed of NaOH and immersing steel in the alkali salt) is increased in temperature and time. Can be considered.
- the formation and removal of Si oxide is affected by the chemical composition of the steel sheet as well as the production conditions such as annealing and pickling. For this reason, in order to ensure brazeability, it is necessary to combine the two appropriately to prevent the concentration of Si oxide in the film.
- Al is added as necessary for the purpose of deoxidation and the like, but Al is concentrated in the film in the finish annealing and pickling processes in the same manner as Si, and remains in the film as an Al oxide to be brazed. There is a possibility of deteriorating.
- Al oxide is formed further inside the Si oxide, that is, when Cr-rich (Fe, Cr) oxide is more stably generated.
- the removal of the Al oxide is basically the same as that of the Si oxide, but it is difficult to remove since the Al oxide is generated inside the Si oxide. Therefore, it is important to suppress the generation, and it is presumed that lowering the annealing temperature and shortening the annealing time are useful.
- the Si cationic fraction Si f in the film preferably is 0.1 or less, more preferably 0.05 or less.
- the Al cation fraction Al f in the film preferably is 0.05 or less, more preferably 0.02 or less. Both are most desirably 0 (below the detection limit).
- the thickness d f of the negative impact film on brazeability is desirable 10 nm, and more desirably from 7nm or less.
- d f is determined by the angle decomposition method. Specifically, measurement is performed by X-ray photoelectron spectroscopy (XPS) at extraction angles of 45 degrees and 90 degrees, and the Cr—O film thickness is obtained from the change in the peak shape of Cr. This is because the oxide film is a mixed oxide of Fe and Cr, and Cr is concentrated on the inner layer side of the film.
- XPS X-ray photoelectron spectroscopy
- the thickness of the surface coating of a stainless steel plate is defined, it is often defined by the thickness until the O peak intensity in the depth direction analysis becomes 1/2 of the maximum intensity.
- Si oxide and Al oxide are contained in the coating, they are present inside the Cr-rich inner layer of the coating.
- the thickness of the film is the same as the thickness until the O peak intensity in the depth direction analysis becomes 1/2 of the maximum intensity.
- the thickness of the film is evaluated to be thicker.
- the Cr cation fraction Cr f in the film is obtained in the same manner as the Si cation fraction Si f and the Al cation fraction Al f . From the viewpoint of solderability Cr f it is preferably set to 0.6 or less. More desirably, it is 0.5 or less.
- d f thickness
- Cr cationic fraction Cr f in the film Si cationic fraction Si f and Al cations fraction Al f of the film.
- the value of d f ⁇ Cr f +5 (Si f + 3Al f ) calculated using these is 2.0 or less, preferably 1.8 or less, more preferably 1.5 or less, and 1. More preferably, it is 3 or less.
- corrosion resistance is also important in this embodiment, and is affected by the composition of the film formed on the surface.
- the value of d f ⁇ Cr f +5 (Si f + 3Al f ) be 0.6 or more, and more preferably 0.7 or more.
- Cr cationic fraction Cr f in the film preferably set to 0.14 or more.
- the present embodiment is made in consideration of the above examination, and provides a ferritic stainless steel sheet having excellent brazing properties, and the gist thereof is as described in the scope of claims. .
- C (C: 0.03% or less) Since C reduces intergranular corrosion resistance and workability, it is necessary to keep the content low. For this reason, the upper limit of the C content is set to 0.03% or less. However, excessively lowering the scouring cost, it is preferable to set the lower limit of the C content to 0.002% or more.
- the upper limit of the C content is preferably 0.02%.
- N (N: 0.05% or less) N is an element useful for pitting corrosion resistance, but its content needs to be kept low in order to reduce intergranular corrosion resistance and workability. For this reason, the upper limit of the N content is set to 0.05% or less. However, since excessively reducing the scouring cost, the lower limit of the N content is preferably set to 0.002% or more. The upper limit of the N content is preferably 0.02%. Furthermore, from the viewpoint of suppressing the coarsening of crystal grains during brazing, the total content of C and N is preferably 0.015% or more ((C + N) ⁇ 0.015%). From the viewpoint of intergranular corrosion resistance and workability, the total content of C and N is preferably 0.05% or less ((C + N) ⁇ 0.05%).
- Si 1% or less Since Si concentrates in the surface film of a stainless steel plate after brazing and contributes to the improvement of corrosion resistance, it is preferable to contain more than 0.1% of Si. Si is useful as a deoxidizing element. However, the addition of an excessive amount facilitates the formation of a film containing Si oxide on the surface of the material before brazing and reduces the workability. Therefore, the Si content is 1% or less, preferably 0.5% or less, more preferably 0.4% or less.
- Mn is an element useful as a deoxidizing element and is preferably contained in an amount of 0.02% or more. However, if an excessive amount is contained, the corrosion resistance is deteriorated, so the Mn content is 1.2% or less, preferably 1% or less, more preferably 0.5% or less. The Mn content is preferably 0.05% or more, and more preferably 0.1% or more.
- Cr 14% or more, 28% or less
- Cr is an element that is fundamental in securing corrosion resistance.
- the combustion exhaust gas flows in the passage, is cooled by cooling water or the like, and is condensed to generate corrosive condensed water. Therefore, the steel plate used for the heat exchanger is required to have corrosion resistance against the exhaust gas condensed water.
- the corrosion resistance with respect to the salt damage from an outer surface is also required. From such a viewpoint, the Cr content needs to be at least 14%.
- the corrosion resistance can be improved as the Cr content is increased, the Cr content is set to 28% or less in order to reduce workability and manufacturability.
- the content of Cr is preferably 16% or more, more preferably 17% or more.
- it is preferable that content of Cr is 23% or less, More preferably, it is 20.5% or less.
- Nb 8 (C + N) or more, 0.8% or less
- Nb is an element useful for fixing C and N and improving the intergranular corrosion resistance of the welded portion
- Nb also improves high temperature strength.
- the heat exchangers targeted in this embodiment there are members through which high-temperature gas flows, but Nb is effective from the viewpoint of strength and thermal fatigue characteristics. In this respect, it is effective to secure Nb in a solid solution state, and it is preferable to contain N (8 (C + N) + 0.03% or more).
- Nb content is 0.8%, preferably 0.6%.
- Al 0.1% or less Since Al has a deoxidizing effect and the like, it is an element useful for scouring and also has an effect of improving moldability. Therefore, Al is preferably contained in an amount of 0.002% or more. However, addition of an excessive amount facilitates formation of a film containing Al oxide on the surface of the material before brazing and deteriorates toughness. For this reason, the Al content is 0.1% or less, preferably 0.08% or less, more preferably 0.05% or less, and still more preferably 0.03% or less.
- the ferritic stainless steel sheet of the present embodiment may further contain at least one of Ni: 5% or less, Cu: 1.5% or less, and Mo: 3% or less in mass%.
- Ni can be contained in an amount of 5% or less as required in order to improve the corrosion resistance.
- Ni has an effect of improving perforation resistance in the corrosion resistance against exhaust gas condensate required for the heat exchangers targeted in the present embodiment and the corrosion resistance against salt damage from the outer surface.
- Ni also has the effect of improving toughness.
- addition of an excessive amount reduces workability and is expensive, leading to an increase in cost.
- Ni content is 0.1% or more, More preferably, it is 0.2% or more, More preferably, it is 0.3% or more. Further, the upper limit of the Ni content is 5%, preferably 3%, more preferably 1.2%.
- Cu can be contained in an amount of 1.5% or less as required in order to improve the corrosion resistance.
- Cu has the effect of improving the perforation resistance like Ni.
- it is preferable that Cu content is 0.1% or more, More preferably, it is 0.2% or more.
- the upper limit of Cu content is 1.5%, preferably 1%.
- Mo Mo can be contained in an amount of 3% or less as required in order to improve the corrosion resistance.
- Mo is effective in improving corrosion resistance and perforation resistance in the corrosion resistance against exhaust gas condensate required for the heat exchangers targeted in the present embodiment and the corrosion resistance against salt damage from the outer surface.
- it is preferable that Mo content is 0.1% or more, More preferably, it is 0.3% or more.
- the upper limit of the Mo content is 3%, preferably 2%.
- the ferritic stainless steel sheet of the present embodiment is further mass%, V: 0.5% or less, W: 1% or less, B: 0.005% or less, Zr: 0.5% or less, Sn: 0.00%. 5% or less, Co: 0.2% or less, Mg: 0.002% or less, Ca: 0.002% or less, REM: 0.01% or less, Sb: 0.5% or less, Ta: 0.5% Any one or more of Ga and 0.01% or less may be contained below.
- V: 0.5% or less V can be contained in an amount of 0.5% or less as required in order to improve the corrosion resistance. Addition of an excessive amount deteriorates processability and increases the cost because it is expensive. V is preferably contained in an amount of 0.5% or less, more preferably 0.3% or less. Moreover, in order to acquire the said effect, it is preferable that V content is 0.05% or more, and it is more preferable that it is 0.1% or more.
- W can be contained in an amount of 1% or less as necessary.
- W has an effect of improving weather resistance and perforation resistance.
- W content is 0.2% or more, More preferably, it is 0.4% or more.
- the upper limit of the W content is 1%, preferably 0.8%.
- B (B: 0.005% or less) B can be contained as necessary in order to improve workability, particularly secondary workability. Addition of an excessive amount reduces intergranular corrosion resistance, so 0.005% or less is preferable. In order to acquire the said effect, it is preferable that B content is 0.0002% or more, More preferably, it is 0.0004% or more. Further, the upper limit of the B content is 0.005%, preferably 0.002%.
- Zr 0.5% or less
- Zr content is 0.05% or more, More preferably, it is 0.1% or more.
- Sn can be contained in an amount of 0.5% or less as required in order to improve the corrosion resistance.
- Sn has an effect of improving the perforation resistance in the corrosion resistance against exhaust gas condensed water and the corrosion resistance against salt damage from the outer surface required for the heat exchangers targeted in the present embodiment.
- excessive addition reduces toughness.
- Sn content is 0.02% or more, More preferably, it is 0.05% or more.
- the upper limit of Sn content is 0.5%, Preferably it is 0.3%.
- Co (Co: 0.2% or less) Co can be contained as necessary in order to improve secondary workability and toughness. Addition of an excessive amount leads to an increase in cost. For this reason, Co is preferably contained in an amount of 0.2% or less, and more preferably 0.15% or less. In order to acquire the said effect, it is preferable that Co content is 0.02% or more, More preferably, it is 0.05% or more.
- Mg is a useful element for scouring because it has a deoxidizing effect and the like. Mg is also effective in improving the workability and toughness by refining the structure. For this reason, 0.002% or less of Mg can be contained as needed. In order to acquire the said effect, it is preferable that Mg content is 0.0002% or more, More preferably, it is 0.0005% or more. Further, the upper limit of the Mg content is 0.002%, preferably 0.0015%.
- Ca is an element useful for scouring because it has a deoxidizing effect and the like, and can contain 0.002% or less of Ca as required.
- the upper limit of the Ca content is 0.002%, preferably 0.0015%.
- REM 0.01% or less
- REM rare earth metal element
- Sc scandium
- Y yttrium
- 15 elements lanthanoid
- La lanthanum
- Lu lutetium
- REM is an element useful for scouring because it has a deoxidizing effect and the like. If necessary, a total of 0.01% or less of REM can be contained. In order to acquire the said effect, it is preferable that REM content is 0.0005% or more, More preferably, it is 0.001% or more. Further, the upper limit of the REM content is 0.01%, preferably 0.008%.
- Sb 0.5% or less
- Sb can be contained in an amount of 0.5% or less as necessary.
- Sb has an effect of improving the perforation resistance.
- the addition of an excessive amount of Sb reduces toughness.
- Sb content is 0.001% or more, More preferably, it is 0.01% or more, Furthermore, it is 0.05% or more. Further, the upper limit of the Sb content is 0.5%, preferably 0.3%.
- Ta can be contained in an amount of 0.5% or less as required in order to improve the corrosion resistance.
- Ta has an effect of improving perforation resistance in the corrosion resistance against exhaust gas condensate required for the heat exchangers targeted in this embodiment and the corrosion resistance against salt damage from the outer surface.
- the addition of an excessive amount of Ta reduces toughness.
- the Ta content is preferably 0.01% or more, further preferably 0.05% or more, and more preferably 0.1% or more. Further, the upper limit of the Ta content is 0.5%, preferably 0.4%.
- Ga forms stable sulfides to improve corrosion resistance and hydrogen embrittlement resistance. Therefore, Ga can be contained in an amount of 0.01% or less as required. In order to acquire the said effect, it is preferable that Ga content is 0.0002% or more, More preferably, it is 0.0005% or more. Moreover, the upper limit of Ga content is 0.01%, Preferably it is 0.005%.
- the P content is preferably 0.04% or less, more preferably 0.035% or less from the viewpoint of weldability.
- the amount of S is preferably 0.02% or less, more preferably 0.01% or less from the viewpoint of corrosion resistance.
- the stainless steel plate of this embodiment can be basically manufactured by a general method for manufacturing a ferritic stainless steel plate.
- molten steel having the above-described chemical composition is obtained in a converter or electric furnace, and scoured in an AOD furnace or a VOD furnace to obtain a steel piece by a continuous casting method or an ingot forming method.
- the steel slab is subjected to the steps of hot rolling, hot-rolled sheet annealing, pickling, cold rolling, finish annealing and pickling to produce a steel plate. If necessary, the annealing of the hot-rolled sheet may be omitted, or the steps of cold rolling, finish annealing and pickling may be repeated.
- the pickling process may be performed by combining a plurality of processes. Specifically, a salt method or a neutral salt electrolysis method is performed as the first step, and nitric acid electrolysis is performed as the second step. As a third step, immersion in nitric hydrofluoric acid may be added. Further, as a second step, immersion in nitric hydrofluoric acid may be performed.
- the salt method is particularly useful for removing the Si oxide, and higher temperature and longer time are more effective. Of these, the longer time will lower the line speed if the equipment is the same. This leads to a decrease in the temperature of the material in front of the salt tank, and decreases the productivity.
- the temperature of the salt method since it is known that the salt deteriorates at 530 ° C. or higher, the steel sheet is usually immersed in a salt at a temperature of about 450 to 480 ° C.
- the temperature in the salt method is set higher than usual.
- the salt temperature is preferably 490 ° C. or higher, more effectively 500 ° C.
- the steel plate is preferably immersed in a temperature range of 500 ° C. or higher and 530 ° C. or lower.
- the immersion time is desirably 2 seconds or more and 10 seconds or less.
- T ⁇ (10t + 2 [Cr]) / 100 ⁇ 600 (where T: temperature (° C.), t: time (sec), [Cr]: Cr content (% by mass)) is satisfied. desirable.
- the salt method is most useful for suppressing the concentration of Si oxide, it is desirable to lower the finish annealing temperature in order to suppress the amount of scale generated itself including the Si oxide.
- the finish annealing temperature is selected according to the chemical composition of the material and the required mechanical properties. In the case of this embodiment, in order to obtain desired mechanical properties, it is effective and desirable to lower by 5 to 20 ° C. from the normal finish annealing temperature. Specifically, the finish annealing temperature is desirably 1000 ° C. or less, and more desirably 970 to 990 ° C. Regarding the lower limit temperature of the finish annealing temperature, it is sufficient that the cold-rolled sheet is finish-annealed to have a metal structure having a recrystallized structure and have desired mechanical properties.
- the heat exchanger of the present embodiment includes a heat exchange part and a case that covers the outside thereof.
- a heat exchange part is produced combining a member.
- the member is produced by forming the ferritic stainless steel plate of the present embodiment into various shapes such as a rectangle, a tube, and a corrugated shape.
- the exhaust gas path and the cooling water path are arranged separately.
- an inlet and an outlet of a pipe through which exhaust gas passes and a pipe through which cooling water passes are arranged.
- the number of members constituting the heat exchange unit is large, and the members have a complicated shape. Many of these members are joined by brazing.
- a brazing material used for brazing Cu brazing and / or Ni brazing is preferably used.
- As for the Ni brazing it is preferable to use a Ni alloy brazing containing Cr or Si.
- This embodiment is intended for brazing a member made of stainless steel using Ni brazing or Cu brazing. Brazing is performed by wetting the members and filling the gaps between the members. When an oxide film is present on the surface of stainless steel constituting the member to be brazed, the member becomes difficult to wet and brazeability is hindered.
- a Cr-rich (Fe, Cr) oxide film (passive film) is formed, thereby exhibiting excellent corrosion resistance.
- the brazing temperature is usually maintained for about 10 to 30 minutes. In such a finite time, how to reduce the coating formed on the surface of the stainless steel has a great influence on the brazeability.
- (Formula 2) is based on the following matters.
- (C) is formed on the surface of the stainless steel (Fe, Cr) oxide film is, the more the film thickness d f is rich in thick Cr, less likely to be reduced.
- (D) When Si oxide or Al oxide that is not reduced under normal brazing conditions is contained in the oxide film, the reducibility of the film is lowered and the brazing property is deteriorated.
- Is formed on the surface (Fe, Cr) is Cr cation fraction Cr f in the oxide film, higher the more stainless steel having Cr content, such as annealing and pickling, manufacturing conditions of the material before being brazed Also affected by.
- the thickness of the oxide film becomes thinner as the stainless steel having a higher Cr content, and is also affected by the material manufacturing conditions. Therefore, the higher the Cr content, the lower the oxide film growth and the thinner the film thickness, so that the above (Equation 2) is satisfied and the brazing property must be ensured.
- Si is contained in the stainless steel in an amount of 1% or less. Si is concentrated in the film in the finish annealing and pickling processes, and remains in the film as Si oxide, which may deteriorate brazing properties. The reason why the Si oxide is concentrated in the film in the finish annealing and pickling processes is not clear, but at present, it is considered as follows. When stainless steel is annealed in the atmosphere, Fe-rich (Fe, Cr) oxide is produced in the outer layer and Cr-rich (Fe, Cr) oxide is produced in the inner layer. And Si can exist as an oxide inside the Cr-rich (Fe, Cr) oxide of the inner layer. Si oxides are more likely to be generated as Cr-rich (Fe, Cr) oxides become more stable.
- the pickling process following the finish annealing is mainly intended to dissolve and remove (Fe, Cr) oxide generated by annealing, and at the same time, a part of the base material is also dissolved.
- Si oxide is stable in the neutral to acidic range. For this reason, it is effective to remove the Si oxide along with the dissolution of the base material or to treat in an alkali capable of dissolving the Si oxide.
- a salt method (a method of heating a commercially available desalting alkali salt mainly composed of NaOH and immersing steel in the alkali salt) and increasing the temperature for a long time. Can be considered.
- the generation and removal of Si oxides are affected by the chemical composition of steel as well as the manufacturing conditions such as annealing and pickling. Therefore, in order to ensure brazing properties, it is preferable to appropriately combine the two to prevent concentration of Si oxide in the film.
- Al is added for the purpose of deoxidation and the like. Like Si, Al is concentrated in the film in the finish annealing and pickling steps, and remains in the film as Al oxide, which may deteriorate the brazing property. Al oxide is formed further inside the Si oxide, that is, when Cr-rich (Fe, Cr) oxide is more stably generated.
- the method for removing the Al oxide is basically the same as the method for removing the Si oxide. However, since Al oxide is generated inside Si oxide, it is difficult to remove. Therefore, it is important to suppress the formation of Al oxide, and it is presumed that lowering the annealing temperature and shortening the annealing time are useful.
- Si oxide and the Al oxide in the coating formed on the surface of the stainless steel adversely affect the brazing property. Therefore, it is necessary to suppress the Si cation fraction Si f and Al cations fraction Al f in the coating low.
- Both the Si cation fraction Si f and the Al cation fraction Al f are determined from the results of quantitative analysis of the outermost surface in X-ray photoelectron spectroscopy (XPS). Note that only cations were used as cations.
- Si cationic fraction Si f in the film is desirably 0.1 or less, more preferably 0.05 or less.
- Al cation fraction Al f in the film is preferably 0.05 or less, more preferably 0.02 or less. Both are most desirably 0 (below the detection limit).
- the thickness d f of the negative impact film on brazeability is desirable 10 nm, and more desirably from 7nm or less.
- d f is determined by the angle decomposition method. Specifically, measurement is performed by X-ray photoelectron spectroscopy (XPS) at extraction angles of 45 degrees and 90 degrees, and the Cr—O film thickness is obtained from the change in the peak shape of Cr. This is because the oxide film is a mixed oxide of Fe and Cr, and Cr is concentrated on the inner layer side of the film.
- XPS X-ray photoelectron spectroscopy
- the thickness of the film formed on the surface of stainless steel it is defined as the thickness until the O peak intensity in the depth direction analysis becomes 1/2 of the maximum intensity.
- Si oxide and Al oxide are contained in the film, these are formed inside the inner layer made of Cr-rich (Fe, Cr) oxide.
- the thickness of the film is the same as the thickness until the O peak intensity in the depth direction analysis becomes 1/2 of the maximum intensity Then, it is evaluated thicker.
- the Cr cation fraction Cr f in the film is obtained in the same manner as the Si cation fraction Si f and the Al cation fraction Al f .
- Cr f is set to 0.5 or less from the viewpoint of brazeability.
- Cr f is desirably 0.45 or less, and more desirably 0.4 or less.
- the upper limit value of the Cr cation fraction Cr f in the film, the film thickness d f , the Si cation fraction Si f , and the preferred range for the Al cation fraction Al f are shown. It was.
- the value of d f ⁇ Cr f +5 (Si f + 3Al f ) is 2.0 or less, preferably 1.8 or less, more preferably 1.5 or less, as shown in (Formula 2). .3 or less is more preferable.
- the present inventors obtained biofuels such as bioethanol and biodiesel, and conducted a detailed investigation and analysis on the oxidative deterioration behavior and the corrosiveness to stainless steel in comparison with ordinary gasoline. As a result, it was found that the fatty acid in the biofuel which was oxidized and deteriorated was distributed to the aqueous phase and developed corrosiveness, and the corrosiveness was expressed by the organic acid concentration corresponding to about 100 times that of gasoline.
- the temperature of the fuel supply system parts close to the engine rises to about 90-100 ° C, and along with the temperature itself, fatty acids are easily distributed from the biofuel to the water phase, and the corrosive environment becomes severe.
- This corrosive environment is a severe condition as compared with a corrosion test (temperature 40 to 50 ° C.) against oxidation-degraded gasoline.
- bioethanol in the biofuel moves to the aqueous phase and enlarges the aqueous phase, and becomes a factor that hinders maintaining a passive state particularly in stainless steel.
- the fuel supply system parts that are placed closer to the engine are better than the fuel pipes and fuel tanks that use ordinary gasoline. Corrosion resistance is required. Therefore, the corrosion resistance of stainless steel in the environment of acidic fatty acid at high temperature was studied earnestly. As a result, the Cr content of the base material is 15% or more, and the Cr cations fraction Cr f in the film was found that there needs to be 0.18 or more. To obtain a more stable corrosion resistance, the Cr content of the base material is 17% or more, and the Cr cations fraction Cr f in the film desirably contains less than 0.20.
- the present embodiment provides a ferritic stainless steel for a fuel supply system member in which the strength is considered in addition to the above knowledge, and the gist thereof is the contents as described in the claims.
- the reason why each composition of the ferritic stainless steel for the fuel supply system member is limited will be described. In the following description, unless otherwise specified,% of each component represents mass%.
- the upper limit of the C content is 0.03% or less, preferably 0.02% or less.
- the lower limit of the C content is preferably 0.002% or more, and more preferably 0.003% or more.
- N (N: 0.05% or less) N is an element useful for pitting corrosion resistance, but its content needs to be kept low in order to reduce intergranular corrosion resistance and workability. For this reason, the upper limit of the N content is 0.05% or less, preferably 0.02% or less. However, excessively reducing the N content increases the scouring cost as well as the required strength cannot be obtained. For this reason, it is preferable that the minimum of content of N shall be 0.002% or more, More preferably, it is 0.003% or more. Furthermore, it is preferable that the total content of C and N is 0.015% or more ((C + N) ⁇ 0.015%) from the viewpoint of suppressing grain coarsening during brazing. From the viewpoint of intergranular corrosion resistance and workability, the total content of C and N is preferably 0.05% or less ((C + N) ⁇ 0.05%).
- Si (Si: 1% or less) Si facilitates the formation of a film containing Si oxide on the surface of the material before brazing and reduces workability. Therefore, the Si content is 1% or less, preferably 0.5% or less, more preferably 0.4% or less. Since Si concentrates on the surface film of stainless steel after brazing and contributes to improvement of corrosion resistance and is useful as a deoxidizing element, the amount of Si is preferably 0.1% or more, more preferably more than 0.1%. is there.
- Mn (Mn: 1.2% or less) Mn deteriorates corrosion resistance. Therefore, the Mn content is 1.2% or less, preferably 1% or less, more preferably 0.5% or less. Mn is an element useful as a deoxidizing element, and preferably contains at least 0.02% or more of Mn. The amount of Mn is more preferably 0.05% or more, and further preferably 0.1%. % Or more.
- Cr 15% or more, 23% or less
- Cr is an element that is fundamental for ensuring corrosion resistance in biofuels. It is necessary to contain at least 15% of Cr, and the amount of Cr is preferably 17% or more. The corrosion resistance can be improved as the Cr content is increased. However, addition of an excessive amount of Cr deteriorates workability and manufacturability. Therefore, the Cr content is 23% or less, preferably 20.5% or less.
- Nb 8 (C + N) + 0.1% or more, 0.8% or less
- Nb is an element useful for fixing C and N and improving the intergranular corrosion resistance of the weld. For this reason, it is necessary to contain Nb at least eight times the (C + N) amount. Further, Nb has a great effect of improving the strength in a solid solution state, so that the strength and fatigue characteristics are improved. From this point, it is effective to secure solid solution Nb. Therefore, Nb must be contained in an amount of 8 (C + N) + 0.1% or more, and the amount of Nb is preferably 8 (C + N) + 0.2% or more. However, the addition of an excessive amount of Nb decreases workability and manufacturability. For this reason, the upper limit of Nb content is 0.8%, preferably 0.6% or less.
- Al (Al: 0.1% or less) Al facilitates the formation of a film containing Al oxide on the surface of the material before brazing and degrades toughness. Therefore, the Al content is 0.1% or less, preferably 0.08% or less, more preferably 0.05% or less, and still more preferably 0.03% or less. Al is a useful element for scouring because it has a deoxidizing effect and the like, and has an effect of improving moldability. Therefore, the Al content is preferably 0.002% or more, and more preferably 0.003% or more.
- the stainless steel of the present embodiment may further contain at least one of Ni: 2% or less, Cu: 1.5% or less, and Mo: 3% or less in mass%.
- Ni Ni can be contained in an amount of 2% or less as required in order to improve the corrosion resistance.
- Ni has the effect of improving the corrosion resistance against salt damage from the outer surface required in the fuel supply system component that is the subject of this embodiment.
- Ni also has the effect of improving strength.
- the amount of Ni is preferably 0.1% or more, more preferably 0.2% or more, and further preferably 0.3% or more.
- the addition of an excessive amount of Ni reduces workability and is expensive, leading to an increase in cost. Therefore, the Ni content is preferably 1.5% or less, and more preferably 1.2% or less.
- Cu can be contained in an amount of 1.5% or less as needed in order to improve the corrosion resistance.
- Cu like Ni, has an effect of improving the corrosion resistance against salt damage from the outer surface required in the fuel supply system component targeted in this embodiment.
- Cu also has the effect of improving strength.
- the amount of Cu is preferably 0.1% or more, more preferably 0.2% or more, and further preferably 0.3% or more.
- the Cu content is preferably 1% or less, and more preferably 0.8% or less.
- Mo Mo can be contained in an amount of 3% or less as required in order to improve the corrosion resistance.
- Mo has the effect of improving the corrosion resistance against salt damage from the outer surface as well as the corrosion resistance in the biofuel required for the fuel supply system parts targeted in the present embodiment.
- Mo also has the effect of improving strength.
- the amount of Mo is preferably 0.1% or more, more preferably 0.3% or more, and further preferably 0.7% or more.
- the addition of an excessive amount of Mo reduces workability and is expensive, leading to an increase in cost. Therefore, the Mo content is preferably 2.2% or less, and more preferably 2% or less.
- V 0.5% or less
- W 1% or less
- B 0.005% or less
- Zr 0.5% or less
- Sn 0.5 % Or less
- Co 0.2% or less
- Mg 0.002% or less
- Ca 0.002% or less
- REM 0.01% or less
- Sb 0.5% or less
- Ta 0.5% or less
- Ga Any one or more of 0.01% or less may be contained.
- V 0.5% or less
- V can be contained in an amount of 0.5% or less as required in order to improve the corrosion resistance.
- the V amount is preferably 0.05% or more, and more preferably 0.1% or more.
- the content of V is preferably 0.3% or less.
- W can be contained in an amount of 1% or less as required.
- W has an effect of improving the corrosion resistance against salt damage from the outer surface required in the fuel supply system component that is the subject of this embodiment.
- the W amount is preferably 0.2% or more, and more preferably 0.5% or more. Addition of an excessive amount of W deteriorates workability and is expensive, leading to an increase in cost. For this reason, the W content is preferably 0.8% or less.
- B can be contained in an amount of 0.005% or less as required in order to improve workability, particularly secondary workability.
- the amount of B is preferably 0.0002% or more, and more preferably 0.0003% or more. Addition of an excessive amount of B reduces intergranular corrosion resistance. For this reason, it is preferable that content of B is 0.0015% or less.
- Zr 0.5% or less
- Zr can be contained in an amount of 0.5% or less as required in order to improve corrosion resistance, particularly intergranular corrosion resistance.
- the amount of Zr is preferably 0.05% or more, and more preferably 0.1% or more. Addition of an excessive amount of Zr deteriorates workability and is expensive, leading to an increase in cost. For this reason, the content of Zr is preferably 0.3% or less.
- Sn can be contained in an amount of 0.5% or less as required in order to improve the corrosion resistance.
- Sn has an effect of improving the perforation resistance in the corrosion resistance against exhaust gas condensed water and the corrosion resistance against salt damage from the outer surface required for the heat exchangers targeted in the present embodiment.
- the Sn content is preferably 0.02% or more, and more preferably 0.05% or more.
- addition of an excessive amount of Sn reduces toughness. For this reason, it is preferable that content of Sn is 0.3% or less.
- Co (Co: 0.2% or less) Co can be contained in an amount of 0.2% or less as required in order to improve secondary workability and toughness.
- the amount of Co is preferably 0.02% or more, and more preferably 0.05% or more.
- the addition of an excessive amount of Co leads to an increase in cost. For this reason, the Co content is preferably 0.15% or less.
- Mg is an element useful for scouring because it has a deoxidizing effect and the like, and is effective in refining the structure and improving workability and toughness. From this, Mg can be contained in an amount of 0.002% or less as required. In order to obtain a stable effect by containing Mg, the amount of Mg is preferably 0.0002% or more, and more preferably 0.0005% or more. The Mg content is preferably 0.0015% or less in order to form sulfides and deteriorate the corrosion resistance.
- Ca is an element useful for scouring because it has a deoxidizing effect and the like, and can be contained in an amount of 0.002% or less as required.
- the Ca content is preferably 0.0002% or more, and more preferably 0.0004% or more.
- the Ca content is preferably 0.0015% or less in order to form sulfides and deteriorate the corrosion resistance.
- REM 0.01% or less
- REM rare earth metal element
- Sc scandium
- Y yttrium
- lanthanoid lanthanum
- Lu lutetium
- REM is an element useful for scouring because it has a deoxidizing effect and the like, and can be contained in an amount of 0.01% or less as required.
- the amount of REM is preferably 0.0005% or more, and more preferably 0.001% or more.
- the REM content is preferably 0.008% or less because it leads to an increase in cost.
- Sb 0.5% or less
- Sb can be contained in an amount of 0.5% or less as necessary.
- Sb has an effect of improving the perforation resistance.
- the addition of an excessive amount of Sb reduces toughness.
- Sb content is 0.001% or more, More preferably, it is 0.01% or more, Furthermore, it is 0.05% or more. Further, the upper limit of the Sb content is 0.5%, preferably 0.3%.
- Ta can be contained in an amount of 0.5% or less as required in order to improve the corrosion resistance.
- Ta has an effect of improving perforation resistance in the corrosion resistance against exhaust gas condensate required for the heat exchangers targeted in this embodiment and the corrosion resistance against salt damage from the outer surface.
- the addition of an excessive amount of Ta reduces toughness.
- the Ta content is preferably 0.01% or more, further preferably 0.05% or more, and more preferably 0.1% or more. Further, the upper limit of the Ta content is 0.5%, preferably 0.4%.
- Ga forms stable sulfides to improve corrosion resistance and hydrogen embrittlement resistance. Therefore, Ga can be contained in an amount of 0.01% or less as required. In order to acquire the said effect, it is preferable that Ga content is 0.0002% or more, More preferably, it is 0.0005% or more. Moreover, the upper limit of Ga content is 0.01%, Preferably it is 0.005%.
- the P content is preferably 0.04% or less, more preferably 0.035% or less from the viewpoint of weldability.
- the amount of S is preferably 0.02% or less, more preferably 0.01% or less from the viewpoint of corrosion resistance.
- the stainless steel of this embodiment is basically manufactured by a general method for manufacturing ferritic stainless steel.
- molten steel having the above-described chemical composition is obtained in a converter or electric furnace, and scoured in an AOD furnace or a VOD furnace to obtain a steel piece by a continuous casting method or an ingot forming method.
- the steel slab is subjected to the steps of hot rolling, hot-rolled sheet annealing, pickling, cold rolling, finish annealing and pickling to produce a steel plate. If necessary, the annealing of the hot-rolled sheet may be omitted, or the steps of cold rolling, finish annealing and pickling may be repeated.
- the pickling process may be performed by combining a plurality of processes. Specifically, a salt method or a neutral salt electrolysis method is performed as the first step, and nitric acid electrolysis is performed as the second step. As a third step, immersion in nitric hydrofluoric acid may be added. Further, as a second step, immersion in nitric hydrofluoric acid may be performed.
- the salt method is particularly useful for removing the Si oxide, and it is effective to increase the temperature and lengthen the time. Of these, the longer time will lower the line speed if the equipment is the same. This leads to a decrease in the temperature of the material in front of the salt tank, and decreases the productivity.
- the temperature of the salt method since it is known that the salt deteriorates at 530 ° C. or higher, the steel sheet is usually immersed in a salt at a temperature of about 450 to 480 ° C.
- the salt temperature is set higher than usual in order to efficiently remove the Si oxide.
- the salt temperature is preferably 490 ° C. or higher, more effectively 500 ° C. or higher, and the steel plate is preferably immersed in a temperature range of 500 ° C. or higher and 530 ° C. or lower.
- the salt immersion time is 2 seconds or more and 10 seconds or less.
- the higher temperature of the salt is likely to lead to deterioration of the surface properties, and the stainless steel having a higher Cr content is more likely to be deteriorated.
- the temperature and immersion time of the salt are T ⁇ (10t + 2 [Cr]) / 100 ⁇ 600 (where T: temperature (° C.), t: immersion time (sec), [Cr]: Cr content ( It is desirable to satisfy mass%)).
- the salt method in the pickling process is most useful for suppressing the concentration of Si oxide.
- the finish annealing temperature is selected according to the chemical composition of the material, the required mechanical properties, and the like. In the case of the present embodiment, it is effective and desirable to lower the temperature by 5 to 20 ° C. from the normal annealing temperature selected for obtaining desired mechanical properties.
- the finish annealing temperature is desirably 1000 ° C. or less, and more desirably 970 to 990 ° C.
- the lower limit temperature of the finish annealing temperature is not limited as long as the cold-rolled sheet is finish-annealed to have a metal structure having a recrystallized structure and have desired mechanical properties.
- the component according to this embodiment includes a brazed member.
- the member is made of the ferritic stainless steel of this embodiment in the shape of a plate, a tube, a rod, or the like, or a processed product thereof. Since the component of this embodiment is formed by brazing and joining members, it can correspond to a component having a complicated shape composed of a large number of members.
- Cu brazing and / or Ni brazing is preferably used as a brazing material. Among these, regarding Ni brazing, Ni alloy brazing containing Cr or Si is preferably used.
- the oxide film present on the surface of the stainless steel is reduced during brazing, and therefore brazing is performed under a condition of a low degree of vacuum or a dew point.
- the brazing temperature is performed under a condition lower than the degree of vacuum or dew point at which Cr and Cr 2 O 3 are in equilibrium.
- the brazing joining can be performed, for example, in a vacuum or in a hydrogen atmosphere at a temperature of 950 to 1200 ° C. for about 10 to 30 minutes.
- argon gas, nitrogen gas, or the like may be used as a gas for atmosphere control or atmosphere replacement.
- Example 1 30 kg of molten steel having the chemical composition shown in Table 1 was melted in a vacuum melting furnace to produce a 17 kg flat steel ingot. Next, the steel ingot was hot rolled to a thickness of 4.5 mm at a heating temperature of 1200 ° C. The hot-rolled sheet was annealed at 950 ° C., and then the scale was removed by alumina shot to cold-roll the hot-rolled sheet to a plate thickness of 1 mm. Thereafter, finish annealing was performed, and the scale was removed by a salt method and immersion in nitric hydrofluoric acid.
- the finish annealing temperature was the temperature shown in Table 1, and the holding time was 1 minute.
- a salt method a method of heating a commercially available desalting alkali salt mainly composed of NaOH and immersing the steel sheet in the alkali salt, the heating temperature was set to the temperature shown in Table 1, and the immersion time was set to 5 seconds.
- nitric hydrofluoric acid a 3% HF-10% HNO 3 solution heated to 55 ° C. was used, and the steel sheet was immersed in this solution for 10 seconds.
- the brazing property was evaluated and the surface film of the material was analyzed.
- Table 2 shows the wax spread coefficient. Note that the wax spreading coefficient is an average value of the three plates. In the present embodiment, the wax spreading coefficient is preferably 2 or more, and more preferably 4 or more.
- XPS X-ray photoelectron spectroscopy
- Table 2 the values of the thickness d f of the oxide film, Cr cationic fraction Cr f, Si cationic fraction Si f, Al cation fraction Al f and d f ⁇ Cr f +5 (Si f + 3Al f) (A value ).
- the example of the present invention in which the value of d f ⁇ Cr f +5 (Si f + 3Al f ) is 2.0 or less has a brazing spread coefficient of 2 or more and is excellent in brazing.
- the brazing spread coefficient becomes less than 2 and the brazing property is inferior.
- Inventive steel 1-3 and comparative steel 1-1 have similar chemical compositions, but a clear difference in the wax spread coefficient is observed.
- the comparative steel 1-1 has a higher Si cation fraction Si f in the film, and the value of d f ⁇ Cr f +5 (Si f + 3Al f ) is 2.0. It is because it exceeded.
- the comparative steel 1-1 has a lower salt temperature, so it is considered that the Si oxide formed in the annealing process could not be removed and was concentrated.
- the comparative steel 1-5 and the inventive steel 1-1 have the same chemical composition. However, in the comparative steel 1-5, the annealing temperature was increased and the salt temperature was lowered, so that d f ⁇ Cr f +5 ( The value of (Si f + 3Al f ) exceeds 2.0. For this reason, compared with the inventive steel 1-1, the comparative steel 1-5 has a greatly reduced brazing coefficient. This is presumably because, in Comparative Steel 1-5, the Si oxide formed in the annealing process was concentrated without being removed.
- Example 2 30 kg of molten steel having the chemical composition shown in Table 3 was melted in a vacuum melting furnace to produce a 17 kg flat steel ingot. Next, the steel ingot was hot rolled to a thickness of 4.5 mm at a heating temperature of 1200 ° C. The obtained hot-rolled sheet was annealed at 950 ° C., then the scale was removed by alumina shot, and the hot-rolled sheet was cold-rolled to a plate thickness of 1 mm. Then, finish annealing was performed with respect to the obtained cold-rolled sheet, and the scale was removed (pickling) by a salt method and immersion in nitric hydrofluoric acid.
- the finish annealing temperature was the temperature shown in Table 4, and the holding time was 1 minute.
- the salt method a method of heating a commercially available alkaline desalting salt mainly composed of NaOH and immersing the steel sheet in the alkaline salt was used. In the salt method, the heating temperature of the salt was set to the temperature shown in Table 4, and the immersion time was 5 seconds. In the nitric hydrofluoric acid immersion, a 3% HF-10% HNO 3 solution heated to 55 ° C. was used, and the steel sheet was immersed in this solution for 10 seconds.
- Inventive steel 2-4 has the same composition as comparative steel 2-6.
- Corrosion tests were conducted under conditions simulating oxidatively degraded biofuel. Two test pieces each having a width of 25 mm and a length of 100 mm were cut out from the cold-rolled steel sheet and degreased using an organic solvent. As the test solution, an aqueous solution in which NaCl was dissolved so that the amount of formic acid was 0.1%, the amount of acetic acid was 1%, and the Cl ion concentration was 100 ppm was used. The test temperature was 95 ° C. and the test time was 168 h. Other test conditions were in accordance with JASO-M611-92-A.
- the corrosion weight loss was determined from the mass change of the test piece before and after the test.
- the presence or absence of local corrosion was determined as shown below using the optical microscope for the entire test piece. That is, the case where a corrosion mark exceeding 10 ⁇ m, which is the detection limit of the corrosion depth measurement value by the depth of focus method, is defined as “local corrosion”, and the case where a corrosion mark exceeding 10 ⁇ m is not detected is defined as “local It was defined as “no corrosion”.
- Table 4 shows the wax spread coefficient. Note that the wax spreading coefficient is an average value of the three plates. In the present embodiment, the wax spreading coefficient is preferably 2 or more, and more preferably 4 or more.
- XPS X-ray photoelectron spectroscopy
- Table 4 the values of the thickness d f of the oxide film, Cr cationic fraction Cr f, Si cationic fraction Si f, Al cation fraction Al f and d f ⁇ Cr f +5 (Si f + 3Al f) (A value ).
- Invention Examples 2-1 to 2-12 have a 0.2% proof stress of 250 MPa or more, no corrosion in a corrosion test under conditions simulating oxidatively deteriorated biofuel, and wax spreading.
- the coefficient is 2 or more, and the brazing property is excellent.
- Comparative Example 2-1 having a Cr content of less than 15% the value of d f ⁇ Cr f +5 (Si f + 3Al f ) is 2.0 or less, but the Cr cation fraction Cr f is less than 0.18. there were. Although it has a wax spreading coefficient of 2 or more, it has poor corrosion resistance in an environment simulating biodegraded biofuel.
- Comparative Examples 2-2, 2-4, and 2-6 in which the value of d f ⁇ Cr f +5 (Si f + 3Al f ) exceeds 2.0, the brazing coefficient is less than 2, and the brazing property is inferior.
- Comparative Example 2-3 since the Cr content is large, the value of d f ⁇ Cr f +5 (Si f + 3Al f ) exceeds 2.0, the Cr cation fraction Crf is increased, and the wax spreading coefficient is 2 It became less than.
- Comparative Example 2-5 since the Nb content in the steel sheet is small, the 0.2% proof stress is less than 250 MPa and the strength is inferior.
- Comparative Example 2-7 since the Cr content was large, the value of d f ⁇ Cr f +5 (Si f + 3Al f ) exceeded 2.0, and the wax spreading coefficient was less than 2.
- the ferritic stainless steel sheet with excellent brazing performance according to the first embodiment is a secondary part of an automobile part such as an EGR cooler, an oil cooler, an exhaust heat recovery unit, a fuel delivery system, or a latent heat recovery type gas water heater.
- an EGR cooler an oil cooler
- an exhaust heat recovery unit a fuel delivery system
- a latent heat recovery type gas water heater a latent heat recovery type gas water heater.
- CO 2 refrigerant heat pump water heaters common name: Ecocute (registered trademark)
- plate type heat exchangers and other heat exchangers such as heat exchangers of various plants, etc. It is suitable as a material.
- the ferritic stainless steel according to the second embodiment is suitable for automobile fuel supply parts, particularly fuel injection parts for direct injection engines that tend to cause pulsation due to fluctuations in fuel pressure, and can be applied regardless of region. is there.
- the ferritic stainless steel according to the second embodiment is a part close to the engine, such as a delivery pipe, a fuel pump part, a fuel pressure adjusting part, etc., among the fuel supply parts. Suitable for parts used below.
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Abstract
Description
本願は、2013年3月29日に日本に出願された特願2013-071740号及び2013年7月17日に日本に出願された特願2013-148951号に基づき優先権を主張し、その内容をここに援用する。
本発明の第1の目的は、熱交換器等ろう付け接合により組み立てられる部材の素材として好適に用いることができる、ろう付け性に優れたフェライト系ステンレス鋼板を提供することである。
本発明の第2の目的は、燃料供給系部材等のろう付け接合により組み立てられる部材の素材として好適に用いることができ、ろう付け性に優れたフェライト系ステンレス鋼板を提供することである。併せて、本発明の第2の目的は、耐食性とろう付け性を両立させ、かつ強度にも優れた燃料供給系部材用フェライト系ステンレス鋼および燃料供給系部品を提供することである。
〔1〕質量%で、C:0.03%以下、N:0.05%以下、Si:1%以下、Mn:1.2%以下、Cr:14%以上28%以下、Nb:8(C+N)以上0.8%以下、及びAl:0.1%以下を含有し、残部がFe及び不可避不純物からなり、表面に式1を満足する皮膜が形成されていることを特徴とするろう付け性に優れたフェライト系ステンレス鋼板。
df×Crf+5(Sif+3Alf)≦2.0 ・・・(式1)
式1において、dfは単位がnmの皮膜の厚さを示し、Crfは皮膜中のCrカチオン分率を示し、Sifは皮膜中のSiカチオン分率を示し、Alfは皮膜中のAlカチオン分率を示す。
〔3〕更に、質量%で、V:0.5%以下、W:1%以下、B:0.005%以下、Zr:0.5%以下、Sn:0.5%以下、Co:0.2%以下、Mg:0.002%以下、Ca:0.002%以下、REM:0.01%以下、Sb:0.5%以下、Ta:0.5%以下、及びGa:0.01%以下のうち何れか1種又は2種以上を含有することを特徴とする〔1〕または〔2〕記載のろう付け性に優れたフェライト系ステンレス鋼板。
df×Crf+5(Sif+3Alf)≦2.0 ・・・(式1)
式1において、dfは単位がnmの皮膜の厚さを示し、Crfは皮膜中のCrカチオン分率を示し、Sifは皮膜中のSiカチオン分率を示し、Alfは皮膜中のAlカチオン分率を示す。
〔7〕更に、質量%で、V:0.5%以下、W:1%以下、B:0.005%以下、Zr:0.5%以下、Sn:0.5%以下、Co:0.2%以下、Mg:0.002%以下、Ca:0.002%以下、REM:0.01%以下、Sb:0.5%以下、Ta:0.5%以下、及びGa:0.01%以下のうち何れか1種又は2種以上を含有することを特徴とする〔5〕または〔6〕記載の熱交換器用フェライト系ステンレス鋼板。
〔8〕質量%で、C:0.03%以下、N:0.05%以下、Si:1%以下、Mn:1.2%以下、Cr:15%以上23%以下、Nb:8(C+N)+0.1%以上0.8%以下、及びAl:0.1%以下を含有し、残部がFe及び不可避不純物からなり、表面に式2および式3を満足する皮膜が形成されていることを特徴とするフェライト系ステンレス鋼。
df×Crf+5(Sif+3Alf)≦2.0 ・・・(式2)
0.18≦Crf≦0.5 ・・・(式3)
式2において、dfは単位がnmの皮膜の厚さを示し、Sifは皮膜中のSiカチオン分率を示し、Alfは皮膜中のAlカチオン分率を示す。式2、式3において、Crfは皮膜中のCrカチオン分率を示す。
〔10〕更に、質量%で、V:0.5%以下、W:1%以下、B:0.005%以下、Zr:0.5%以下、Sn:0.5%以下、Co:0.2%以下、Mg:0.002%以下、Ca:0.002%以下、REM:0.01%以下、Sb:0.5%以下、Ta:0.5%以下、及びGa:0.01%以下のうち何れか1種以上を含有することを特徴とする〔8〕または〔9〕記載のフェライト系ステンレス鋼。
df×Crf+5(Sif+3Alf)≦2.0 ・・・(式2)
0.18≦Crf≦0.5 ・・・(式3)
式2において、dfは単位がnmの皮膜の厚さを示し、Sifは皮膜中のSiカチオン分率を示し、Alfは皮膜中のAlカチオン分率を示す。式2、式3において、Crfは皮膜中のCrカチオン分率を示す。
〔14〕更に、質量%で、V:0.5%以下、W:1%以下、B:0.005%以下、Zr:0.5%以下、Sn:0.5%以下、Co:0.2%以下、Mg:0.002%以下、Ca:0.002%以下、REM:0.01%以下、Sb:0.5%以下、Ta:0.5%以下、及びGa:0.01%以下のうち何れか1種又は2種以上を含有することを特徴とする〔12〕または〔13〕記載の燃料供給系部材用フェライト系ステンレス鋼。
(第1の実施形態)
本実施形態は、NiろうやCuろうを用いてろう付け接合される部材の素材として用いられるフェライト系ステンレス鋼板を対象としている。ろう付けは、950~1200℃において真空中もしくは水素雰囲気中で行われる。このとき、雰囲気制御や置換用としてアルゴンガスや窒素ガス等が併用される場合がある。ろう付けでは、ろうが母材(素材)にぬれてすきまを充填し、これにより母材が接合される。素材の表面に酸化皮膜が存在すると、ぬれにくくなりろう付け性が阻害される。
その結果、ろう付け性に優れたフェライト系ステンレス鋼板を得るには、表面に形成される皮膜が、以下に示す(式1)を満足する必要があることを知見した。
df×Crf+5(Sif+3Alf)≦2.0 ・・・(式1)
(式1)において、dfは皮膜の厚さ(nm)を示し、Crfは皮膜中のCrカチオン分率を示し、Sifは皮膜中のSiカチオン分率を示し、Alfは皮膜中のAlカチオン分率を示す。
(a)ステンレス鋼板の表面に形成されている(Fe、Cr)酸化物皮膜は、膜厚が厚くCrに富むほど、還元されにくい。
(b)通常、Si酸化物やAl酸化物はろう付け条件にて還元されないので、皮膜中に含まれると、皮膜の還元性を低下させ、ろう付け性を劣化させる。
Siカチオン分率SifおよびAlカチオン分率Alfの両者は、X線光電子分光法(XPS)における最表面の定量分析結果から求められる。なお、カチオンは金属元素のみを対象とする。皮膜中のSiカチオン分率Sifは0.1以下が望ましく、より望ましくは0.05以下である。皮膜中のAlカチオン分率Alfは0.05以下が望ましく、より望ましくは0.02以下である。両者とも最も望ましくは0(検出限界以下)である。
Cは、耐粒界腐食性、加工性を低下させるため、その含有量を低く抑える必要がある。このため、Cの含有量の上限を0.03%以下とする。しかしながら、過度に低めることは精練コストを上昇させるため、Cの含有量の下限を0.002%以上とすることが好ましい。Cの含有量の上限は好ましくは0.02%である。
Nは、耐孔食性に有用な元素であるが、耐粒界腐食性、加工性を低下させるため、その含有量を低く抑える必要がある。このため、Nの含有量の上限を0.05%以下とする。しかしながら、過度に低めることは精練コストを上昇させるため、Nの含有量の下限を0.002%以上とすることが好ましい。Nの含有量の上限は好ましくは0.02%である。さらに、ろう付け時の結晶粒の粗大化を抑制する観点から、CとNの合計含有量を0.015%以上((C+N)≧0.015%)とするのが好ましい。また、耐粒界腐食性および加工性の観点から、CとNの合計含有量を0.05%以下((C+N)≦0.05%)とするのが好ましい。
Siは、ろう付け後にステンレス鋼板の表面皮膜に濃化して耐食性の向上に寄与するために、0.1%超のSiを含有させることが好ましい。また、Siは、脱酸元素として有用である。しかしながら、過剰な量の添加は、ろう付け前の素材の表面にSi酸化物を含有する皮膜を形成させやすくすると共に加工性を低下させる。このため、Siの含有量を1%以下とし、好ましくは0.5%以下、より好ましくは0.4%以下とする。
Mnは、脱酸元素として有用な元素であり、0.02%以上含有させることが好ましい。しかしながら、過剰の量を含有させると耐食性を劣化させるので、Mnの含有量を1.2%以下とし、好ましくは1%以下、より好ましくは0.5%以下とする。Mnの含有量は、0.05%以上であることが好ましく、0.1%以上であることがより好ましい。
Crは、耐食性を確保する上で基本となる元素である。本実施形態で対象としている熱交換器類では、多くの場合、燃焼排ガスが経路内を流れ、冷却水等により冷却されて結露し、腐食性の凝縮水が生成する。そのため熱交換器に用いる鋼板には排ガス凝縮水に対する耐食性が求められる。また、屋外で使用される熱交換器の場合には、外面からの塩害に対する耐食性も必要である。このような観点から、Crの含有量は少なくとも14%以上必要である。Crの含有量を増加させるほど耐食性を向上させることができるが、加工性、製造性を低下させるためCr量を28%以下とする。Crの含有量は、好ましくは16%以上、より好ましくは17%以上である。また、Crの含有量は、23%以下であることが好ましく、より好ましくは20.5%以下である。
Nbは、CおよびNを固定し、溶接部の耐粒界腐食性を向上させる上で有用な元素であるため、(C+N)量の8倍以上含有させる必要がある。また、Nbは高温強度を向上させる。本実施形態で対象とする熱交換器のなかには高温のガスが流れる部材があるが、強度ならびに熱疲労特性の観点からNbは有効である。この点から固溶状態のNbを確保するのは有効であり、8(C+N)+0.03%以上のNbを含有させるのが好ましい。しかしながら、過剰量の添加は、加工性、製造性を低下させるため、Nbの含有量の上限は0.8%であり、好ましくは0.6%である。
Alは、脱酸効果等を有するので精練上有用な元素であり、成形性を向上させる効果もある。そのため、Alは0.002%以上含有させることが好ましい。しかしながら、過剰量の添加は、ろう付け前の素材の表面にAl酸化物を含有する皮膜を形成させやすくすると共に靭性を劣化させる。このため、Alの含有量を0.1%以下、好ましくは0.08%以下、より好ましくは0.05%以下、さらに好ましくは0.03%以下とする。
(Ni:5%以下)
Niは、耐食性を向上させるために、必要に応じて5%以下含有させることができる。特に、本実施形態で対象としている熱交換器類に要求される排ガス凝縮水に対する耐食性や外面からの塩害に対する耐食性において、Niは耐孔あき性を向上させる効果を有する。また、Niは靭性を向上させる効果も有する。しかし、過剰量の添加は、加工性を低下させるとともに高価なためコストアップにもつながる。Ni含有量は、上記効果を得るために0.1%以上であることが好ましく、より好ましくは0.2%以上であり、さらに好ましくは0.3%以上である。また、Ni含有量の上限は、5%であり、好ましくは3%であり、より好ましくは1.2%である。
Cuは、耐食性を向上させるために、必要に応じて1.5%以下含有させることができる。特に、本実施形態で対象としている熱交換器類に要求される排ガス凝縮水に対する耐食性や外面からの塩害に対する耐食性において、Cuは、Niと同様に、耐孔あき性を向上させる効果を有する。しかし、過剰量の添加は加工性を低下させる。Cu含有量は、上記効果を得るために0.1%以上であることが好ましく、より好ましくは0.2%以上である。また、Cu含有量の上限は、1.5%であり、好ましくは1%である。
Moは、耐食性を向上させるために、必要に応じて3%以下含有させることができる。特に、Moは、本実施形態で対象としている熱交換器類に要求される排ガス凝縮水に対する耐食性や外面からの塩害に対する耐食性において、Moは、耐銹性ならびに耐孔あき性を向上させる効果を有する。しかし、過剰量の添加は、加工性を低下させるとともに高価なためコストアップにもつながる。Mo含有量は、上記効果を得るために0.1%以上であることが好ましく、より好ましくは0.3%以上である。また、Mo含有量の上限は、3%であり、好ましくは2%である。
(V:0.5%以下)
Vは、耐食性を向上させるために、必要に応じて0.5%以下含有させることができる。過剰量の添加は、加工性を劣化させると共に、高価であるためコストアップにつながる。Vは、0.5%以下含有させることが好ましく、0.3%以下含有させることがより好ましい。また、上記効果を得るために、V含有量は、0.05%以上であることが好ましく、0.1%以上であることがより好ましい。
Wは、耐食性を向上させるために、必要に応じて1%以下含有させることができる。特に、本実施形態で対象としている熱交換器類に要求される排ガス凝縮水に対する耐食性や外面からの塩害に対する耐食性において、Wは耐銹性ならびに耐孔あき性を向上させる効果を有する。しかし、過剰量の添加は、加工性を劣化させると共に、高価であるためコストアップにつながる。W含有量は、上記効果を得るために、0.2%以上であることが好ましく、より好ましくは0.4%以上である。また、W含有量の上限は、1%であり、好ましくは0.8%である。
Bは、加工性、特に二次加工性を向上させるために、必要に応じて含有させることができる。過剰量の添加は耐粒界腐食性を低下させるので0.005%以下含有させるのが好ましい。B含有量は、上記効果を得るために、0.0002%以上であることが好ましく、より好ましくは0.0004%以上である。また、B含有量の上限は、0.005%であり、好ましくは0.002%である。
Zrは、耐食性、特に耐粒界腐食性を向上させるために、必要に応じて含有させることができる。過剰量の添加は、加工性を劣化させると共に、高価であるためコストアップにつながる。このため、0.5%以下含有させることが好ましく、0.3%以下含有させることがより好ましい。また、Zr含有量は、上記効果を得るために、0.05%以上であることが好ましく、より好ましくは0.1%以上である。
Snは、耐食性を向上させるために、必要に応じて0.5%以下含有させることができる。特に、本実施形態で対象としている熱交換器類に要求される排ガス凝縮水に対する耐食性や外面からの塩害に対する耐食性において、Snは耐孔あき性を向上させる効果を有する。しかし、過剰量の添加は靭性を低下させる。Sn含有量は、上記効果を得るために、0.02%以上であることが好ましく、より好ましくは0.05%以上である。また、Sn含有量の上限は、0.5%であり、好ましくは0.3%である。
Coは、二次加工性と靭性を向上させるために、必要に応じて含有させることができる。過剰量の添加はコストアップにつながる。このためCoは0.2%以下含有させるのが好ましく、0.15%以下含有させることがより好ましい。Co含有量は、上記効果を得るために、0.02%以上であることが好ましく、より好ましくは0.05%以上である。
Mgは、脱酸効果等を有するので精練に有用な元素である。またMgは組織を微細化し加工性や靭性の向上にも効果がある。このため、必要に応じて0.002%以下のMgを含有させることができる。Mg含有量は、上記効果を得るために、0.0002%以上であることが好ましく、より好ましくは0.0005%以上である。また、Mg含有量の上限は、0.002%であり、好ましくは0.0015%である。
Caは、脱酸効果等を有するので精練に有用な元素であり、必要に応じて0.002%以下のCaを含有させることができる。Ca含有量は、上記効果を得るために、0.0002%以上であることが好ましく、より好ましくは0.0005%以上である。また、Ca含有量の上限は、0.002%であり、好ましくは0.0015%である。
REM(希土類金属元素)は、一般的な定義に従い、スカンジウム(Sc)、イットリウム(Y)の2元素と、ランタン(La)からルテチウム(Lu)までの15元素(ランタノイド)の総称を指す。単独で添加してもよいし、混合物であってもよい。REMは、脱酸効果等を有するので精練に有用な元素である。必要に応じて合計で0.01%以下のREMを含有させることができる。REM含有量は、上記効果を得るために、0.0005%以上であることが好ましく、より好ましくは0.001%以上である。また、REM含有量の上限は、0.01%であり、好ましくは0.008%である。
Sbは、耐食性を向上させるために、必要に応じて0.5%以下の量で含有させることができる。特に、本実施形態で対象としている熱交換器類に要求される排ガス凝縮水に対する耐食性や外面からの塩害に対する耐食性において、Sbは耐孔あき性を向上させる効果を有する。しかし、過剰量のSbの添加は靭性を低下させる。Sb含有量は、上記効果を得るために、0.001%以上であることが好ましく、より好ましくは0.01%以上、さらに0.05%以上である。また、Sb含有量の上限は、0.5%であり、好ましくは0.3%である。
Taは、耐食性を向上させるために、必要に応じて0.5%以下の量で含有させることができる。特に、本実施形態で対象としている熱交換器類に要求される排ガス凝縮水に対する耐食性や外面からの塩害に対する耐食性において、Taは耐孔あき性を向上させる効果を有する。しかし、過剰量のTaの添加は靭性を低下させる。Ta含有量は、上記効果を得るために、0.01%以上が好ましく、さらに0.05%以上であることが好ましく、より好ましくは0.1%以上である。また、Ta含有量の上限は、0.5%であり、好ましくは0.4%である。
Gaは、安定な硫化物を形成して耐食性を向上させるとともに耐水素脆化性も向上させることから、必要に応じて0.01%以下の量で含有させることができる。Ga含有量は、上記効果を得るために、0.0002%以上であることが好ましく、より好ましくは0.0005%以上である。また、Ga含有量の上限は、0.01%であり、好ましくは0.005%である。
本実施形態において、酸洗工程は複数の工程を組み合わせて行ってもよい。具体的には、第一の工程としてソルト法もしくは中性塩電解法を行い、第二の工程として硝酸電解を行う。第三工程として、硝ふっ酸への浸漬が追加される場合がある。また、第二工程として、硝ふっ酸への浸漬を行ってもよい。
ソルト法の温度に関しては、ソルトの劣化が530℃以上で起こることが知られているため、通常450~480℃程度の温度のソルトに鋼板は浸漬される。しかし、本実施形態の場合、通常よりもソルト法での温度を高く設定する。具体的には、ソルトの温度を490℃以上とすることが好ましく、500℃以上とするとより効果的であり、500℃以上530℃以下の温度範囲で鋼板を浸漬することが望ましい。
浸漬時間は2秒以上10秒以下とすることが望ましい。ただし、ソルトの高温化は、表面性状の劣化につながりやすく、かつCr含有量の多いステンレス鋼板ほど劣化しやすい。このため、T×(10t+2[Cr])/100≦600(ここで、T:温度(℃)、t:時間(sec)、[Cr]:Cr含有量(質量%))を満足することが望ましい。
本実施形態の熱交換器は、熱交換部と、その外側を覆うケースを備える。熱交換部は、部材を組み合わせて作製される。部材は、本実施形態のフェライト系ステンレス鋼板を、矩形、管状、波形などの各種形状に成形して作製されたものである。熱交換部では、排ガスの経路と冷却水の経路が分かれて配置される。熱交換器の外側には、排ガスが通る管と冷却水が通る管のそれぞれの入口と出口が配置される。本実施形態の熱交換器では、熱交換部を構成する部材の数が多数であり、かつ部材は複雑な形状を有する。この部材の多くは、ろう付けによって接合されている。ろう付けに用いられるろう材としては、Cuろうおよび/またはNiろうが用いられることが好ましい。Niろうについては、CrやSiを含有したNi合金ろうが用いられることが好ましい。
まず、ろう付け性について説明する。本実施形態は、NiろうもしくはCuろうを用いたステンレス鋼からなる部材のろう付けを対象としている。ろうが部材をぬらして部材間のすきまを充填することにより接合されるのがろう付けである。ろう付けされる部材を構成するステンレス鋼の表面に酸化皮膜が存在すると、部材がぬれにくくなり、ろう付け性を阻害する。
その結果、ろう付け性を得るには、表面に形成される皮膜が、以下に示す(式2)を満足するとともに、皮膜中のCrカチオン分率を0.5以下にする必要があることを知見した。
df×Crf+5(Sif+3Alf)≦2.0 ・・・(式2)
(式2)において、dfは皮膜の厚さ(nm)を示し、Crfは皮膜中のCrカチオン分率を示し、Sifは皮膜中のSiカチオン分率を示し、Alfは皮膜中のAlカチオン分率を示す。
(c)ステンレス鋼の表面に形成されている(Fe、Cr)酸化物皮膜が、膜厚dfが厚くCrに富むほど、還元されにくい。
(d)通常のろう付け条件では還元されないSi酸化物やAl酸化物が酸化物皮膜中に含まれると、皮膜の還元性を低下させ、ろう付け性を劣化させる。
ステンレス鋼を大気中で焼鈍すると、外層にFeリッチな(Fe、Cr)酸化物が生成し、内層にCrリッチな(Fe、Cr)酸化物が生成する。そして、内層のCrリッチな(Fe、Cr)酸化物の内側に、Siが酸化物として存在しうる。Si酸化物は、Crリッチな(Fe、Cr)酸化物が安定なほど生成しやすい。このため、母材要因としては、Cr含有量の多いステンレス鋼ほど、Si酸化物が生成しやすいと推察される。また、製造プロセス要因としては、焼鈍温度が高いほど、焼鈍時間が長いほど、Si酸化物が生成しやすいと推察される。
Siカチオン分率SifおよびAlカチオン分率Alfの両者は、X線光電子分光法(XPS)における最表面の定量分析結果から求められる。なお、カチオンは金属元素のみを対象とした。皮膜中のSiカチオン分率Sifは、0.1以下が望ましく、より望ましくは0.05以下である。皮膜中のAlカチオン分率Alfは、0.05以下が望ましく、より望ましくは0.02以下である。両者とも最も望ましくは0(検出限界以下)である。
df×Crf+5(Sif+3Alf)の値は、(式2)に示すように2.0以下とされ、1.8以下とするのが好ましく、1.5以下がさらに好ましく、1.3以下にするとより好ましい。
そこで、高温で酸性脂肪酸の環境中でのステンレス鋼の耐食性について鋭意検討した。その結果、母材のCr量を15%以上とし、かつ皮膜中のCrカチオン分率Crfを0.18以上とする必要があることがわかった。より安定した耐食性を得るには、母材のCr量を17%以上とし、かつ皮膜中のCrカチオン分率Crfを0.20以上含有することが望ましい。
以下、燃料供給系部材用フェライト系ステンレス鋼の各組成を限定した理由について説明する。なお、以下の説明では、特に断らない限り、各成分の%は、質量%を表すものとする。
Cは、耐粒界腐食性、加工性を低下させるため、その含有量を低く抑える必要がある。このため、Cの含有量の上限を0.03%以下とし、好ましくは0.02%以下とする。しかしながら、Cの含有量を過度に低めると、必要な強度が得られなくなるとともに精練コストを上昇させる。このため、Cの含有量の下限を0.002%以上とすることが好ましく、より好ましくは0.003%以上とする。
Nは、耐孔食性に有用な元素であるが、耐粒界腐食性、加工性を低下させるため、その含有量を低く抑える必要がある。このため、Nの含有量の上限を0.05%以下とし、好ましくは0.02%以下とする。しかしながら、Nの含有量を過度に低めることは、必要な強度が得られなくなるとともに精練コストを上昇させる。このため、Nの含有量の下限を0.002%以上とすることが好ましく、より好ましくは0.003%以上である。
さらに、ろう付け時の結晶粒粗大化抑制の観点から、CとNの合計含有量を0.015%以上((C+N)≧0.015%)とするのが好ましい。また、耐粒界腐食性および加工性の観点から、CとNの合計含有量を0.05%以下((C+N)≦0.05%)とするのが好ましい。
Siは、ろう付け前の素材の表面にSi酸化物を含有する皮膜を形成させやすくすると共に加工性を低下させる。このため、Siの含有量を1%以下とし、好ましくは0.5%以下、より好ましくは0.4%以下とする。Siは、ろう付け後にステンレス鋼の表面皮膜に濃化して耐食性の向上に寄与すると共に脱酸元素として有用なため、Si量は0.1%以上が好ましく、より好ましくは0.1%超である。
Mnは、耐食性を劣化させる。このため、Mnの含有量を1.2%以下とし、好ましくは1%以下、より好ましくは0.5%以下とする。Mnは、脱酸元素として有用な元素であり、少なくとも0.02%以上のMnを含有させることが好ましく、Mn量は、より好ましくは、0.05%以上であり、さらに好ましくは0.1%以上である。
Crは、バイオ燃料中での耐食性を確保するために基本となる元素である。Crは、少なくとも15%以上含有させることが必要であり、Cr量は好ましくは17%以上である。Crの含有量を増加させるほど耐食性を向上させることができる。しかし、過剰な量のCrの添加は加工性、製造性を低下させる。このため、Crの含有量を23%以下とし、好ましくは20.5%以下とする。
Nbは、CおよびNを固定し、溶接部の耐粒界腐食性を向上させるために有用な元素である。このため、Nbを(C+N)量の8倍以上含有させる必要がある。また、Nbは固溶状態で強度を向上させる効果が大きいので、強度ならびに疲労特性を向上させる。この点から固溶状態のNbを確保するのは有効である。したがって、Nbは、8(C+N)+0.1%以上の量で含有させる必要があり、Nb量は好ましくは8(C+N)+0.2%以上である。しかしながら、過剰量のNbの添加は、加工性、製造性を低下させる。このため、Nbの含有量の上限を0.8%とし、好ましくは0.6%以下である。
Alは、ろう付け前の素材の表面にAl酸化物を含有する皮膜を形成させやすくすると共に靭性を劣化させる。このため、Alの含有量を0.1%以下とし、好ましくは0.08%以下、より好ましくは0.05%以下、さらに好ましくは0.03%以下とする。Alは、脱酸効果等を有するので精練のために有用な元素であり、成形性を向上させる効果もある。そのため、Al量は0.002%以上が好ましく、より好ましくは0.003%以上である。
(Ni:2%以下)
Niは、耐食性を向上させるために、必要に応じて2%以下含有させることができる。特に、Niは、本実施形態で対象としている燃料供給系部品において要求される外面からの塩害に対する耐食性を向上させる効果を有する。また、Niは、強度を向上させる効果も有する。このため、Niを含有させる場合、Ni量は、0.1%以上が好ましく、より好ましくは0.2%以上であり、さらに好ましくは0.3%以上である。しかし、過剰量のNiの添加は、加工性を低下させるとともに高価なためコストアップにもつながる。したがって、Ni含有量は、1.5%以下であることが好ましく、1.2%以下であることがより好ましい。
Cuは、耐食性を向上させるために、必要に応じて1.5%以下の量で含有させることができる。Cuは、Niと同様、特に、本実施形態で対象としている燃料供給系部品において要求される外面からの塩害に対する耐食性を向上させる効果を有する。また、Cuは、強度を向上させる効果も有する。このため、Cuを含有させる場合、Cu量は0.1%以上が好ましく、より好ましくは0.2%以上であり、さらに好ましくは0.3%以上である。しかし、過剰量の添加は加工性を低下させる。したがって、Cu含有量は、1%以下であることが好ましく、さらに好ましくは0.8%以下である。
Moは、耐食性を向上させるために、必要に応じて3%以下含有させることができる。Moは、特に、本実施形態で対象としている燃料供給系部品において要求されるバイオ燃料中での耐食性と共に、外面からの塩害に対する耐食性を向上させる効果を有する。また、Moは、強度を向上させる効果も有する。このため、Moを含有させる場合、Mo量は0.1%以上が好ましく、より好ましくは0.3%以上であり、さらに好ましくは0.7%以上である。しかし、過剰量のMoの添加は、加工性を低下させるとともに高価なためコストアップにもつながる。したがって、Mo含有量は、2.2%以下であることが好ましく、さらに好ましくは2%以下である。
(V:0.5%以下)
Vは、耐食性を向上させるために、必要に応じて0.5%以下含有させることができる。Vを含有することによる安定した効果を得るには、V量は0.05%以上が好ましく、0.1%以上がより好ましい。しかし、過剰量のVの添加は、加工性を劣化させると共に、高価であるためコストアップにつながる。このため、Vの含有量は、0.3%以下であることが好ましい。
Wは、耐食性を向上させるために、必要に応じて1%以下の量で含有させることができる。Wは、特に、本実施形態で対象としている燃料供給系部品において要求される外面からの塩害に対する耐食性を向上させる効果を有する。Wを含有することによる安定した効果を得るには、W量は、0.2%以上が好ましく、0.5%以上がより好ましい。過剰量のWの添加は、加工性を劣化させると共に、高価であるためコストアップにつながる。このため、Wの含有量は、0.8%以下であることが好ましい。
Bは、加工性、特に二次加工性を向上させるために、必要に応じて0.005%以下の量で含有させることができる。Bを含有することによる安定した効果を得るには、B量は、0.0002%以上が好ましく、0.0003%以上がより好ましい。過剰量のBの添加は耐粒界腐食性を低下させる。このため、Bの含有量は、0.0015%以下であることが好ましい。
Zrは、耐食性、特に耐粒界腐食性を向上させるために、必要に応じて0.5%以下の量で含有させることができる。Zrを含有することによる安定した効果を得るには、Zr量は、0.05%以上が好ましく、0.1%以上がより好ましい。過剰量のZrの添加は、加工性を劣化させると共に、高価であるためコストアップにつながる。このため、Zrの含有量は、0.3%以下であることが好ましい。
Snは、耐食性を向上させるために、必要に応じて0.5%以下の量で含有させることができる。特に、本実施形態で対象としている熱交換器類に要求される排ガス凝縮水に対する耐食性や外面からの塩害に対する耐食性において、Snは耐孔あき性を向上させる効果を有する。Snを含有することによる安定した効果を得るには、Sn量は、0.02%以上が好ましく、0.05%以上がより好ましい。しかし、過剰量のSnの添加は靭性を低下させる。このため、Snの含有量は、0.3%以下であることが好ましい。
Coは、二次加工性と靭性を向上させるために、必要に応じて0.2%以下の量で含有させることができる。Coを含有することによる安定した効果を得るには、Co量は、0.02%以上が好ましく、0.05%以上がより好ましい。しかし、過剰量のCoの添加はコストアップにつながる。このため、Coの含有量は、0.15%以下であることが好ましい。
Mgは、脱酸効果等を有するので精練に有用な元素であり、組織を微細化し加工性や靭性の向上にも効果がある。このことから、Mgは、必要に応じて0.002%以下の量で含有させることができる。Mgを含有することによる安定した効果を得るには、Mg量は、0.0002%以上が好ましく、0.0005%以上がより好ましい。Mg含有量は、硫化物を形成して耐食性を劣化させるため、0.0015%以下とすることが好ましい。
Caは、脱酸効果等を有するので精練に有用な元素であり、必要に応じて0.002%以下の量で含有させることができる。Caを含有することによる安定した効果を得るには、Ca量は、0.0002%以上が好ましく、0.0004%以上がより好ましい。Ca含有量は、硫化物を形成して耐食性を劣化させるため、0.0015%以下とすることが好ましい。
REM(希土類金属元素)は、一般的な定義に従い、スカンジウム(Sc)、イットリウム(Y)の2元素と、ランタン(La)からルテチウム(Lu)までの15元素(ランタノイド)の総称を指す。単独で添加してもよいし、混合物であってもよい。REMは、脱酸効果等を有するので精練に有用な元素であり、必要に応じて0.01%以下の量で含有させることができる。REMを含有することによる安定した効果を得るには、REM量は、0.0005%以上が好ましく、0.001%以上がより好ましい。REM含有量は、コストアップにつながるため、0.008%以下とすることが好ましい。
Sbは、耐食性を向上させるために、必要に応じて0.5%以下の量で含有させることができる。特に、本実施形態で対象としている熱交換器類に要求される排ガス凝縮水に対する耐食性や外面からの塩害に対する耐食性において、Sbは耐孔あき性を向上させる効果を有する。しかし、過剰量のSbの添加は靭性を低下させる。Sb含有量は、上記効果を得るために、0.001%以上であることが好ましく、より好ましくは0.01%以上、さらに0.05%以上である。また、Sb含有量の上限は、0.5%であり、好ましくは0.3%である。
Taは、耐食性を向上させるために、必要に応じて0.5%以下の量で含有させることができる。特に、本実施形態で対象としている熱交換器類に要求される排ガス凝縮水に対する耐食性や外面からの塩害に対する耐食性において、Taは耐孔あき性を向上させる効果を有する。しかし、過剰量のTaの添加は靭性を低下させる。Ta含有量は、上記効果を得るために、0.01%以上が好ましく、さらに0.05%以上であることが好ましく、より好ましくは0.1%以上である。また、Ta含有量の上限は、0.5%であり、好ましくは0.4%である。
Gaは、安定な硫化物を形成して耐食性を向上させるとともに耐水素脆化性も向上させることから、必要に応じて0.01%以下の量で含有させることができる。Ga含有量は、上記効果を得るために、0.0002%以上であることが好ましく、より好ましくは0.0005%以上である。また、Ga含有量の上限は、0.01%であり、好ましくは0.005%である。
また、S量については、耐食性の観点から0.02%以下とすることが好ましく、より好ましくは0.01%以下である。
本実施形態において、酸洗工程は複数の工程を組み合わせて行ってもよい。具体的には、第一の工程としてソルト法もしくは中性塩電解法を行い、第二の工程として硝酸電解を行う。第三工程として、硝ふっ酸への浸漬が追加される場合がある。また、第二工程として、硝ふっ酸への浸漬を行ってもよい。
ソルト法の温度に関しては、ソルトの劣化が530℃以上で起こることが知られているため、通常450~480℃程度の温度のソルトに鋼板は浸漬される。しかし、本実施形態の場合、Si酸化物を効率よく除去するために、ソルトの温度を通常より高く設定する。具体的には、ソルトの温度を490℃以上とすることが好ましく、500℃以上とするとより効果的であり、500℃以上530℃以下の温度範囲で鋼板を浸漬することが望ましい。
ろう付け接合には、ろう材としてCuろうおよび/またはNiろうが用いられることが好ましい。このうちNiろうについては、CrやSiを含有したNi合金ろうが用いられることが好ましい。
表1に示す化学組成を有する溶鋼30kgを真空溶解炉にて溶製して17kgの扁平鋼塊を作製した。次いで、加熱温度1200℃にて厚さ4.5mmまで鋼塊を熱延した。950℃にて熱延板の焼鈍を行い、次いで、アルミナショットによりスケールを除去して板厚1mmまで熱延板を冷延した。その後、仕上焼鈍を行い、ソルト法および硝ふっ酸への浸漬によりスケールを除去した。
ソルト法としては、NaOHを主成分とする市販のデスケール用アルカリソルトを加熱して鋼板をアルカリソルトに浸漬する方法を用い、加熱温度を表1に示す温度とし、浸漬時間を5秒とした。
硝ふっ酸への浸漬においては、55℃に加熱した3%HF-10%HNO3溶液を用い、鋼板をこの溶液に10秒間浸漬した。こうして得られた冷延鋼板(発明鋼1-1~1-12、比較鋼1-1~1-5)を用いて、ろう拡がり性を評価すると共に素材の表面皮膜を分析した。
冷延鋼板より幅40mm、長さ40mmの板を3枚ずつ切り出し、有機溶剤を用いて脱脂した。次いで、板の中央に0.5gの純Cuろう(BCu-1)を載せ、真空炉に入れ、1130℃にて10分加熱した。真空度は約50Paであった。加熱後に冷却し、ろうの寸法を測定した。寸法を測定した結果より、ろう面積を求め、次の式より、ろう拡がり係数を算出した。
ろう拡がり係数=熱処理後のろう面積/初期ろう面積
X線光電子分光法(XPS)により、素材の表面皮膜を分析した。XPSはアルバック・ファイ社製である。使用X線源にmono-AlKα線を用い、X線ビーム径が約100μmであり、取り出し角が45度と90度である条件で実施した。XPSにおける最表面の定量分析結果から、Crカチオン分率Crf、Siカチオン分率SifおよびAlカチオン分率Alfを求めた。ここでカチオンは金属元素のみを対象とした。また、酸化皮膜の厚さdfは、角度分解法により求めた。
比較例に示すようにdf×Crf+5(Sif+3Alf)の値が2.0を超えると、ろう拡がり係数が2未満となり、ろう付け性に劣る。
表3に示す化学組成を有する溶鋼30kgを真空溶解炉にて溶製して17kgの扁平鋼塊を作製した。次いで、加熱温度1200℃にて厚さ4.5mmまで鋼塊を熱延した。得られた熱延板に対して950℃にて熱延板の焼鈍を行い、次いで、アルミナショットによりスケールを除去し、板厚1mmまで熱延板を冷延した。その後、得られた冷延板に対して仕上げ焼鈍を行い、ソルト法および硝ふっ酸への浸漬によりスケールを除去(酸洗)した。
ソルト法としては、NaOHを主成分とする市販のデスケール用アルカリソルトを加熱して鋼板をアルカリソルトに浸漬する方法を用いた。ソルト法では、ソルトの加熱温度を表4に示す温度とし、浸漬時間を5秒とした。
硝ふっ酸浸漬においては、55℃に加熱した3%HF-10%HNO3溶液を用い、鋼板をこの溶液に10秒間浸漬した。
こうして得られた冷延鋼板(発明鋼2-1~2-12、比較鋼2-1~2-7)を用いて、強度、耐食性、ろう拡がり性を評価すると共に、素材の表面皮膜を分析した。なお、発明鋼2-4は、比較鋼2-6と同じ組成である。
冷延鋼板よりJIS13B号試験片をL方向に採取し、常温で引張試験を行った。得られた0.2%耐力を、表4に示す。
酸化劣化したバイオ燃料を模擬した条件にて腐食試験を行った。冷延鋼板より、それぞれ幅25mm、長さ100mmの試験片を2枚ずつ切り出し、有機溶剤を用いて脱脂した。試験溶液には、ギ酸の量が0.1%、酢酸の量が1%であり、Clイオン濃度が100ppmになるようにNaClを溶解させた水溶液を用いた。試験温度は95℃とし、試験時間は168hとした。これら以外の試験条件については、JASO-M611-92-Aに準じた。
冷延鋼板より幅40mm、長さ40mmの板を3枚ずつ切り出し、有機溶剤を用いて脱脂した。次いで、板の中央に0.5gの純Cuろう(BCu-1)を載せ、真空炉に入れ、1130℃にて10分間加熱した。真空度は約50Paであった。加熱後に冷却し、ろうの寸法を測定した。寸法測定結果より、ろう面積を求め、次の式より、ろう拡がり係数を算出した。
ろう拡がり係数=熱処理後ろう面積/初期ろう面積
X線光電子分光法(XPS)により、素材の表面皮膜を分析した。XPSはアルバック・ファイ社製である。使用X線源にmono-AlKα線を用い、X線ビーム径が約100μmであり、取り出し角が45度と90度である条件で実施した。XPSにおける最表面の定量分析結果から、Crカチオン分率Crf、Siカチオン分率SifおよびAlカチオン分率Alfを求めた。ここでカチオンは金属元素のみを対象とした。また、酸化皮膜の厚さdfは、角度分解法により求めた。
Cr含有量が15%未満の比較例2-1は、df×Crf+5(Sif+3Alf)の値が2.0以下であるが、Crカチオン分率Crfが0.18未満であった。ろう拡がり係数は2以上あるものの、酸化劣化したバイオ燃料を模擬した環境での耐食性に劣る。
df×Crf+5(Sif+3Alf)の値が2.0を超えている比較例2-2,2-4および2-6は、ろう拡がり係数が2未満となり、ろう付け性に劣る。
比較例2-3は、Cr含有量が多いため、df×Crf+5(Sif+3Alf)の値が2.0を超えるとともに,Crカチオン分率Crfが大きくなり、ろう拡がり係数が2未満となった。
比較例2-5は、鋼板中のNb含有量が少ないため、0.2%耐力が250MPa未満と強度に劣る。
比較例2-7は、Cr含有量が多いため,df×Crf+5(Sif+3Alf)の値が2.0を超え、ろう拡がり係数が2未満となった。
Claims (14)
- 質量%で、
C:0.03%以下、
N:0.05%以下、
Si:1%以下、
Mn:1.2%以下、
Cr:14%以上28%以下、
Nb:8(C+N)以上0.8%以下、及び
Al:0.1%以下を含有し、
残部がFe及び不可避不純物からなり、
表面に式1を満足する皮膜が形成されていることを特徴とするろう付け性に優れたフェライト系ステンレス鋼板。
df×Crf+5(Sif+3Alf)≦2.0 ・・・(式1)
式1において、dfは単位がnmの皮膜の厚さを示し、Crfは皮膜中のCrカチオン分率を示し、Sifは皮膜中のSiカチオン分率を示し、Alfは皮膜中のAlカチオン分率を示す。 - 更に、質量%で、Ni:5%以下、Cu:1.5%以下、Mo:3%以下のうち何れか1種以上を含有することを特徴とする請求項1記載のろう付け性に優れたフェライト系ステンレス鋼板。
- 更に、質量%で、V:0.5%以下、W:1%以下、B:0.005%以下、Zr:0.5%以下、Sn:0.5%以下、Co:0.2%以下、Mg:0.002%以下、Ca:0.002%以下、REM:0.01%以下、Sb:0.5%以下、Ta:0.5%以下、及びGa:0.01%以下のうち何れか1種以上を含有することを特徴とする請求項1または2記載のろう付け性に優れたフェライト系ステンレス鋼板。
- ろう付け接合された部材からなる熱交換部を備え、
前記部材は、請求項1~請求項3のいずれか一項に記載のフェライト系ステンレス鋼板からなることを特徴とする熱交換器。 - 質量%で、
C:0.03%以下、
N:0.05%以下、
Si:1%以下、
Mn:1.2%以下、
Cr:14%以上28%以下、
Nb:8(C+N)以上0.8%以下、及び
Al:0.1%以下を含有し、
残部がFe及び不可避不純物からなり、
表面に式1を満足する皮膜が形成されていることを特徴とする熱交換器用フェライト系ステンレス鋼板。
df×Crf+5(Sif+3Alf)≦2.0 ・・・(式1)
式1において、dfは単位がnmの皮膜の厚さを示し、Crfは皮膜中のCrカチオン分率を示し、Sifは皮膜中のSiカチオン分率を示し、Alfは皮膜中のAlカチオン分率を示す。 - 更に、質量%で、Ni:5%以下、Cu:1.5%以下、Mo:3%以下のうち何れか1種以上を含有することを特徴とする請求項5記載の熱交換器用フェライト系ステンレス鋼板。
- 更に、質量%で、V:0.5%以下、W:1%以下、B:0.005%以下、Zr:0.5%以下、Sn:0.5%以下、Co:0.2%以下、Mg:0.002%以下、Ca:0.002%以下、REM:0.01%以下、Sb:0.5%以下、Ta:0.5%以下、及びGa:0.01%以下のうち何れか1種以上を含有することを特徴とする請求項5または6記載の熱交換器用フェライト系ステンレス鋼板。
- 質量%で、
C:0.03%以下、
N:0.05%以下、
Si:1%以下、
Mn:1.2%以下、
Cr:15%以上23%以下、
Nb:8(C+N)+0.1%以上0.8%以下、及び
Al:0.1%以下を含有し、
残部がFe及び不可避不純物からなり、
表面に式2および式3を満足する皮膜が形成されていることを特徴とするフェライト系ステンレス鋼。
df×Crf+5(Sif+3Alf)≦2.0 ・・・(式2)
0.18≦Crf≦0.5 ・・・(式3)
式2において、dfは単位がnmの皮膜の厚さを示し、Sifは皮膜中のSiカチオン分率を示し、Alfは皮膜中のAlカチオン分率を示す。式2、式3において、Crfは皮膜中のCrカチオン分率を示す。 - 更に、質量%で、Ni:2%以下、Cu:1.5%以下、Mo:3%以下のうち何れか1種以上を含有することを特徴とする請求項8記載のフェライト系ステンレス鋼。
- 更に、質量%で、V:0.5%以下、W:1%以下、B:0.005%以下、Zr:0.5%以下、Sn:0.5%以下、Co:0.2%以下、Mg:0.002%以下、Ca:0.002%以下、REM:0.01%以下、Sb:0.5%以下、Ta:0.5%以下、及びGa:0.01%以下のうち何れか1種以上を含有することを特徴とする請求項8または9記載のフェライト系ステンレス鋼。
- ろう付け接合された部材を備え、
前記部材は、請求項8~10のいずれか一項に記載のフェライト系ステンレス鋼からなることを特徴とする燃料供給系部品。 - 質量%で、
C:0.03%以下、
N:0.05%以下、
Si:1%以下、
Mn:1.2%以下、
Cr:15%以上23%以下、
Nb:8(C+N)+0.1%以上0.8%以下、及び
Al:0.1%以下を含有し、
残部がFe及び不可避不純物からなり、
表面に式2および式3を満足する皮膜が形成されていることを特徴とする燃料供給系部材用フェライト系ステンレス鋼。
df×Crf+5(Sif+3Alf)≦2.0 ・・・(式2)
0.18≦Crf≦0.5 ・・・(式3)
式2において、dfは単位がnmの皮膜の厚さを示し、Sifは皮膜中のSiカチオン分率を示し、Alfは皮膜中のAlカチオン分率を示す。式2、式3において、Crfは皮膜中のCrカチオン分率を示す。 - 更に、質量%で、Ni:2%以下、Cu:1.5%以下、Mo:3%以下のうち何れか1種以上を含有することを特徴とする請求項12記載の燃料供給系部材用フェライト系ステンレス鋼。
- 更に、質量%で、V:0.5%以下、W:1%以下、B:0.005%以下、Zr:0.5%以下、Sn:0.5%以下、Co:0.2%以下、Mg:0.002%以下、Ca:0.002%以下、REM:0.01%以下、Sb:0.5%以下、Ta:0.5%以下、及びGa:0.01%以下のうち何れか1種以上を含有することを特徴とする請求項12または13記載の燃料供給系部材用フェライト系ステンレス鋼。
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| CN201480011445.8A CN105008590B (zh) | 2013-03-29 | 2014-03-24 | 钎焊性优良的铁素体系不锈钢板、热交换器、热交换器用铁素体系不锈钢板、铁素体系不锈钢、燃料供给体系构件用铁素体系不锈钢及燃料供给体系部件 |
| EP14773798.5A EP2980274B8 (en) | 2013-03-29 | 2014-03-24 | Ferritic stainless steel sheet having excellent brazeability, heat exchanger, ferritic stainless steel sheet for heat exchangers, ferritic stainless steel, ferritic stainless steel for members of fuel supply systems, and member of fuel supply system |
| JP2015508499A JP6270821B2 (ja) | 2013-03-29 | 2014-03-24 | ろう付け性に優れたフェライト系ステンレス鋼板、熱交換器、熱交換器用フェライト系ステンレス鋼板、フェライト系ステンレス鋼、燃料供給系部材用フェライト系ステンレス鋼、及び燃料供給系部品 |
| US14/770,680 US10131977B2 (en) | 2013-03-29 | 2014-03-24 | Ferritic stainless steel sheet having excellent brazability, heat exchanger, ferritic stainless steel sheet for heat exchangers, ferritic stainless steel, ferritic stainless steel for members of fuel supply systems, and member of fuel supply system |
| KR1020157023461A KR101703464B1 (ko) | 2013-03-29 | 2014-03-24 | 브레이징성이 우수한 페라이트계 스테인리스 강판, 열 교환기, 열 교환기용 페라이트계 스테인리스 강판, 페라이트계 스테인리스강, 연료 공급계 부재용 페라이트계 스테인리스강 및 연료 공급계 부품 |
| ES14773798T ES2784303T3 (es) | 2013-03-29 | 2014-03-24 | Chapa de acero inoxidable ferrítico que tiene excelente soldabilidad, intercambiador de calor, chapa de acero inoxidable ferrítico para intercambiadores de calor, acero inoxidable ferrítico, acero inoxidable ferrítico para elementos de sistemas de suministro de combustible y elemento del sistema de suministro de combustible |
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|---|---|---|---|
| JP2013-071740 | 2013-03-29 | ||
| JP2013071740 | 2013-03-29 | ||
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| JP2013-148951 | 2013-07-17 |
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| PCT/JP2014/058112 Ceased WO2014157104A1 (ja) | 2013-03-29 | 2014-03-24 | ろう付け性に優れたフェライト系ステンレス鋼板、熱交換器、熱交換器用フェライト系ステンレス鋼板、フェライト系ステンレス鋼、燃料供給系部材用フェライト系ステンレス鋼、及び燃料供給系部品 |
Country Status (7)
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|---|---|
| US (1) | US10131977B2 (ja) |
| EP (1) | EP2980274B8 (ja) |
| JP (1) | JP6270821B2 (ja) |
| KR (1) | KR101703464B1 (ja) |
| CN (1) | CN105008590B (ja) |
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| JP2016151038A (ja) * | 2015-02-17 | 2016-08-22 | 日新製鋼株式会社 | 硫酸イオンと塩化物イオンを含んだ環境における耐食性に優れたプラント用途向けフェライト系ステンレス鋼製プラント部材 |
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| JP2016183400A (ja) * | 2015-03-26 | 2016-10-20 | 新日鐵住金ステンレス株式会社 | バーリング加工部端面の耐食性に優れるフェライト系ステンレス鋼板およびその製造方法 |
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| JP2018115359A (ja) * | 2017-01-17 | 2018-07-26 | 日新製鋼株式会社 | 潜熱回収型熱交換器用ステンレス鋼 |
| JP2018172735A (ja) * | 2017-03-31 | 2018-11-08 | 新日鐵住金ステンレス株式会社 | ろう付け性と耐食性に優れたフェライト系ステンレス鋼およびNiろう付け接合部材 |
| WO2019151125A1 (ja) * | 2018-01-31 | 2019-08-08 | Jfeスチール株式会社 | フェライト系ステンレス鋼 |
| JP6624347B1 (ja) * | 2018-01-31 | 2019-12-25 | Jfeスチール株式会社 | フェライト系ステンレス鋼 |
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| JP2021055141A (ja) * | 2019-09-30 | 2021-04-08 | 日鉄ステンレス株式会社 | フェライト系ステンレス鋼 |
| JP7341016B2 (ja) | 2019-09-30 | 2023-09-08 | 日鉄ステンレス株式会社 | フェライト系ステンレス冷延鋼板 |
| JP2023139754A (ja) * | 2022-03-22 | 2023-10-04 | 日鉄ステンレス株式会社 | フェライト系ステンレス鋼板およびその製造方法 |
| JP2024009497A (ja) * | 2022-07-11 | 2024-01-23 | 日鉄ステンレス株式会社 | フェライト系ステンレス鋼板とその製造方法 |
| JP7801583B2 (ja) | 2022-07-11 | 2026-01-19 | 日本製鉄株式会社 | フェライト系ステンレス鋼板とその製造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2980274A4 (en) | 2017-04-05 |
| CN105008590A (zh) | 2015-10-28 |
| JPWO2014157104A1 (ja) | 2017-02-16 |
| EP2980274B8 (en) | 2020-04-22 |
| US10131977B2 (en) | 2018-11-20 |
| EP2980274B1 (en) | 2020-03-18 |
| EP2980274A1 (en) | 2016-02-03 |
| CN105008590B (zh) | 2017-09-19 |
| US20160002760A1 (en) | 2016-01-07 |
| KR101703464B1 (ko) | 2017-02-06 |
| ES2784303T3 (es) | 2020-09-24 |
| JP6270821B2 (ja) | 2018-01-31 |
| KR20150110800A (ko) | 2015-10-02 |
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