JP2011032514A - 窒素化合物層を有する鉄鋼部材、及びその製造方法 - Google Patents
窒素化合物層を有する鉄鋼部材、及びその製造方法 Download PDFInfo
- Publication number
- JP2011032514A JP2011032514A JP2009178497A JP2009178497A JP2011032514A JP 2011032514 A JP2011032514 A JP 2011032514A JP 2009178497 A JP2009178497 A JP 2009178497A JP 2009178497 A JP2009178497 A JP 2009178497A JP 2011032514 A JP2011032514 A JP 2011032514A
- Authority
- JP
- Japan
- Prior art keywords
- compound layer
- treatment
- nitriding
- nitrogen
- chemical conversion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910017464 nitrogen compound Inorganic materials 0.000 title claims abstract description 66
- 150000002830 nitrogen compounds Chemical class 0.000 title claims abstract description 66
- 239000010959 steel Substances 0.000 title claims abstract description 61
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 48
- 230000008569 process Effects 0.000 title abstract description 6
- 238000011282 treatment Methods 0.000 claims abstract description 100
- 238000005121 nitriding Methods 0.000 claims abstract description 62
- 239000000126 substance Substances 0.000 claims abstract description 60
- 238000010438 heat treatment Methods 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000000463 material Substances 0.000 claims abstract description 57
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 18
- 239000010410 layer Substances 0.000 claims description 128
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 59
- 230000006698 induction Effects 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 23
- 239000002131 composite material Substances 0.000 claims description 15
- 229910000734 martensite Inorganic materials 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000002344 surface layer Substances 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- 150000004673 fluoride salts Chemical class 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 150000004679 hydroxides Chemical class 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims 1
- 229910052711 selenium Inorganic materials 0.000 claims 1
- 239000011669 selenium Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 238000007739 conversion coating Methods 0.000 abstract 1
- 238000010791 quenching Methods 0.000 description 27
- 230000000171 quenching effect Effects 0.000 description 27
- 230000000694 effects Effects 0.000 description 24
- 239000007788 liquid Substances 0.000 description 18
- 230000001681 protective effect Effects 0.000 description 17
- 239000011572 manganese Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 239000011651 chromium Substances 0.000 description 8
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 8
- 229910000165 zinc phosphate Inorganic materials 0.000 description 8
- 229910000975 Carbon steel Inorganic materials 0.000 description 7
- 239000010962 carbon steel Substances 0.000 description 7
- 150000004767 nitrides Chemical class 0.000 description 7
- 229910000851 Alloy steel Inorganic materials 0.000 description 6
- 238000005255 carburizing Methods 0.000 description 5
- 229910000760 Hardened steel Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- 229910001337 iron nitride Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 229910001566 austenite Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910001562 pearlite Inorganic materials 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 102200082816 rs34868397 Human genes 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000005496 tempering Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- 229910017119 AlPO Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910000669 Chrome steel Inorganic materials 0.000 description 1
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- 229910015475 FeF 2 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000617 Mangalloy Inorganic materials 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- QDLZHJXUBZCCAD-UHFFFAOYSA-N [Cr].[Mn] Chemical compound [Cr].[Mn] QDLZHJXUBZCCAD-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 238000009661 fatigue test Methods 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical group 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 102200094897 rs121913558 Human genes 0.000 description 1
- 102220061996 rs786203944 Human genes 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
Classifications
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
- C23C8/42—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions only one element being applied
- C23C8/48—Nitriding
- C23C8/50—Nitriding of ferrous surfaces
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/80—After-treatment
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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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/06—Surface hardening
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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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/06—Surface hardening
- C21D1/09—Surface hardening by direct application of electrical or wave energy; by particle radiation
- C21D1/10—Surface hardening by direct application of electrical or wave energy; by particle radiation by electric induction
-
- 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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/78—Combined heat-treatments not provided for above
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/24—Nitriding
- C23C8/26—Nitriding of ferrous surfaces
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
- C23C8/38—Treatment of ferrous surfaces
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
- C23C8/52—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions more than one element being applied in one step
- C23C8/54—Carbo-nitriding
- C23C8/56—Carbo-nitriding of ferrous surfaces
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
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Abstract
【解決手段】鉄鋼材料に対して窒化処理と高周波焼入れ処理との組み合わせ複合熱処理を施す方法において、窒化処理後高周波焼入れ処理前に、窒化処理により鉄鋼に形成された窒素化合物層上に化成皮膜を形成させる化成処理工程を更に含むことを特徴とする方法。
【選択図】図1
Description
このうち、窒化処理により最表面に形成される窒化物からなる化合物層は、摺動性に優れており、摩耗に強く、焼き付き抵抗性が高いことが知られている(以下、これを窒素化合物層による効果Iと呼ぶ)。しかし、一般的に窒化処理は、浸炭焼入れ、高周波焼入れに比較して、面圧強度、疲労強度等において劣っており、例えばローラーピッチング試験を行った場合、窒素化合物層が鋼素地より剥離を生じる場合がある。その為、窒素化合物層は2GPaを越えるような高面圧における疲労試験においては、むしろ悪影響を与える存在であると広く信じられていた。本発明者等は、この要因は化合物層そのものにあるのでは無く、化合物層を支える素地の硬化層深さが浅いためであることを見出した。すなわち、窒化処理単体では、最表面の化合物層の良好な摺動性を十分に生かす為には、その直下の硬化層深さが不足していたのである。
焼入れによって得られた窒素含有のマルテンサイト組織は、上述の高硬度や焼入れ性向上の他に、焼き戻し軟化抵抗性、亀裂発生・成長に対する抵抗故の高面圧強度、高疲労強度を有することが知られている。
高周波焼入れ前の窒化処理により得られる窒素化合物層の厚さは特に限定されないが、通常は1〜30μmの厚さで形成されていれば良く、さらに好ましくは2〜20μmであり、さらに好ましくは3〜15μmである。
750℃以下の加熱では窒素が入っているとは言え、この温度では十分にオーステナイト化されないため焼入れ不十分となる。加熱が860℃を上回る温度では、化合物層直下のマルテンサイト組織中に過剰な残留オーステナイトが発生しやすくなるため好ましく無い。加熱時間が0.3秒未満の加熱では窒素が拡散しているとは言え、十分にオーステナイト化されないため焼入れ不十分となる。5秒を上回る加熱時間では、もはや加熱時間の効果がほぼ飽和する上、化合物層保護膜の作用が低下するため好ましく無い。
本発明の化合物層保護膜を用いることにより、高周波加熱時の雰囲気が大気中であっても、窒素化合物層は酸化や分解から十分に抑制される。また、設備導入が可能であれば、高周波加熱時の雰囲気は、真空雰囲気、アルゴンガスや窒素ガスによる不活性雰囲気、低酸素雰囲気、炭化水素系の還元性雰囲気、アンモニアガス雰囲気等で行うこともできる。
高周波加熱時、処理物が大きい場合などは、予備加熱を含めた多段の昇温法を適宜行うことができる。高周波加熱による焼入れ後は、通常の焼入れ手法と同様に適当な条件にて焼き戻し処理を行っても良い。
先に述べたように本発明の適用対象となる鉄鋼材料は、窒素による効果IIの焼入れ性向上作用の為、必ずしも調質鋼を用いる必要は無く、非調質鋼であるフェライト−パーライト組織の鋼でも十分な機械強度を得られる。また合金鋼の方がやや高い表面硬度が得られる傾向はあるものの、窒素による効果IIにより、安価な炭素鋼であっても十分に深い硬化深さが得られる。例えば、S45Cなどの機械構造用炭素鋼においても、十分な硬度、かつ十分な深さの硬度プロファイルを持つ熱処理材となる。また、そのS45Cでさえ、必ずしも調質材である必要は無く、非調質のフェライト−パーライト組織の鋼部材に本発明の熱処理を適用しても、十分なマルテンサイト変態を生じ、十分な機械的強度を有する熱処理機械部品となりえる。
以上のように本発明の適用により、部品の機械強度の向上、切削工程の低減や安価な材料への切り替えによって、部品の小型化による機械部品全体の小型・軽量化、および窒化処理と高周波焼入れとの複合処理によるコスト増を補って余るだけの実質コストの低減が可能となる。
基材として直径8mm、長さ50mmのSCM440調質材を使用し、この表面を脱脂洗浄したのち、溶融塩浴中において560℃で1時間塩浴軟窒化処理(イソナイト処理:日本パーカライジング(株)製)して油冷し、鋼材表面に厚さ約7μmの窒化鉄を主体とする窒素化合物層を形成した。これに対し、表面調整液(PL-55;日本パーカライジング製)に浸漬することによって表面調整を行った後、りん酸マンガン化成処理液(PF-M1A;日本パーカライジング製)に浸漬し95℃にて1分間の化成処理を行った。化成皮膜は主にりん酸、Mn、Feを含有する結晶質のものであり、2.8g/m2の皮膜量であった。化成処理後の化合物層の厚さは約5μmであった。これに大気雰囲気中で高周波焼入れ装置を使用して、0.8秒の加熱によって860℃に到達後、直ちに水冷して焼入れを行った。
基材として直径8mm、長さ50mmのS45C調質材を使用し、この表面を脱脂洗浄したのち、溶融塩浴中において560℃で2時間塩浴軟窒化処理(イソナイト処理:日本パーカライジング(株)製)して油冷し、鋼材表面に厚さ約13μmの窒化鉄を主体とする窒素化合物層を形成した。これに対し、ジルコニウム系化成処理液(PLC−2000;日本パーカライジング製)に浸漬し45℃にて5分間の化成処理を行った。化成皮膜は主にZr、Fe、フッ化物、水酸化物を含有する非晶質のものであり、0.3g/m2の皮膜量であった。化成処理後の窒素化合物層の厚さは約13μmであり、化成処理による化合物層の厚さに変化はほとんど見られなかった。これに高周波焼入れ装置を使用して、1秒の加熱によって820℃に到達後、直ちに水冷して焼入れを行った。
基材として直径8mm、長さ50mmのSCM435調質材を使用し、この表面を脱脂洗浄したのち、溶融塩浴中において560℃で2時間塩浴軟窒化処理(イソナイト処理:日本パーカライジング(株)製)して水冷し、鋼材表面に厚さ約10μmの窒化鉄を主体とする窒素化合物層を形成した。これに対し、表面調整液(PL-XG;日本パーカライジング製)に浸漬することによって表面調整を行った後、りん酸亜鉛化成処理液(PB-L47;日本パーカライジング製)に浸漬し50℃にて10分間の化成処理を行った。化成皮膜は主にりん酸、Zn、Feを含有する結晶質のものであり、1.2g/m2の皮膜量であった。化成処理後の化合物層厚さは約9μmであった。これに大気雰囲気中で高周波焼入れ装置を使用して、1秒間の加熱によって820℃に到達後、直ちに水冷して焼入れを行った。
基材として直径8mm、長さ50mmのSCM440調質材を使用し、この表面を脱脂洗浄したのち、溶融塩浴中において560℃で1時間塩浴軟窒化処理(イソナイト処理:日本パーカライジング(株)製)して油冷し、鋼材表面に厚さ約7μmの窒化鉄を主体とする窒素化合物層を形成した。これに大気雰囲気中で高周波焼入れ装置を使用して、0.8秒の加熱によって860℃に到達後、直ちに水冷して焼入れを行った。
これらの処理を行った鋼材をマイクロカッターで切断し、樹脂中に埋め込み、金属顕微鏡により断面観察を行った。また、この埋め込みサンプルを用いて、マイクロビッカース硬度計を用いて断面硬度測定を行った。
Claims (8)
- 鉄鋼材料に対して窒化処理と高周波焼入れ処理との組み合わせ複合熱処理を施す方法において、窒化処理後高周波焼入れ処理前に、窒化処理により鉄鋼に形成された窒素化合物層上に化成皮膜を形成させる化成処理工程を更に含むことを特徴とする方法。
- 前記方法が、化成皮膜により高周波焼入れ時の窒素化合物層の分解を抑制することで、窒化処理によって形成された硬度HV550以上かつ1μm以上の窒素化合物層が表層に残存し、その層の下部に窒素を含有する微細マルテンサイト組織を含むHV550を越える硬度分布領域が表面からの距離で200μm以上存在する鉄鋼材料を得る方法であることを特徴とする複合熱処理方法。
- 前記化成皮膜が、皮膜量として0.1〜50g/m2であることを特徴とする請求項1又は2に記載の複合熱処理方法。
- 前記化成皮膜が、金属としてFe、Cr、Ni、Al、Zn、Mn、Mg、Zr、V、Hf、SiおよびCaからなる群の中から選択される少なくとも1種の金属と、りん酸塩、炭酸塩、酸化物、水酸化物およびフッ化物からなる群から選択される少なくとも1種の化合物とを含有することを特徴とする請求項1〜3のいずれか一項に記載の複合熱処理方法。
- 前記窒素化合物層の形成方法が塩浴軟窒化処理、ガス窒化処理、ガス軟窒化処理又はプラズマ窒化処理のいずれかによって行われ、その処理によって鋼材の表面に1〜30μmの窒素を含有する化合物層が形成されることを特徴とする請求項1〜4のいずれか一項に記載の複合熱処理方法。
- 窒化処理の温度が350〜600℃であり、高周波焼入れ時の到達温度が750〜860℃であることを特徴とする請求項1〜5のいずれか一項に記載の複合熱処理方法。
- 請求項1〜6のいずれか一項に記載の複合熱処理によって得られる、硬度HV550以上かつ1μm以上の窒素化合物層が表層に残存し、その層の下部に窒素を含有する微細マルテンサイト組織を含むHV550を越える硬度分布領域が表面からの距離で200μm以上存在することを特徴とする鉄鋼部材。
- 窒素と鉄とを含有する化合物層表面のエッチングを駆動力として析出する成分、過飽和により析出する成分又は外部電源を用いた電気的駆動力により析出する成分を含有する化成処理液であって、鉄鋼材料の窒化処理後高周波焼入れ処理前に、窒化処理により鉄鋼材料上に形成された前記化合物層の分解防止のために当該化合物層上に化成皮膜を形成するために使用される化成処理液。
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- 2010-07-28 EP EP10804113.8A patent/EP2460906A4/en not_active Withdrawn
- 2010-07-28 WO PCT/JP2010/004782 patent/WO2011013362A1/ja active Application Filing
- 2010-07-28 KR KR1020127005034A patent/KR20120051048A/ko not_active Application Discontinuation
- 2010-07-28 CN CN2010800336898A patent/CN102471865A/zh active Pending
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US9429216B2 (en) | 2011-02-23 | 2016-08-30 | Ntn Corporation | Chain guide and chain tensioner device |
JP2015059248A (ja) * | 2013-09-19 | 2015-03-30 | 新日鐵住金株式会社 | 鋼の熱処理方法 |
JP2019035111A (ja) * | 2017-08-16 | 2019-03-07 | パーカー熱処理工業株式会社 | 鉄鋼部材及びその製造方法 |
WO2023234362A1 (ja) * | 2022-06-01 | 2023-12-07 | パーカー加工株式会社 | 摺動部材 |
CN115094368A (zh) * | 2022-06-30 | 2022-09-23 | 安徽聚力石油钻采设备科技有限公司 | 一种免喷涂柱塞的制备方法 |
CN115094368B (zh) * | 2022-06-30 | 2024-02-09 | 安徽聚力石油钻采设备科技有限公司 | 一种免喷涂柱塞的制备方法 |
Also Published As
Publication number | Publication date |
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US20120118434A1 (en) | 2012-05-17 |
JP5328545B2 (ja) | 2013-10-30 |
WO2011013362A1 (ja) | 2011-02-03 |
EP2460906A1 (en) | 2012-06-06 |
KR20120051048A (ko) | 2012-05-21 |
CN102471865A (zh) | 2012-05-23 |
EP2460906A4 (en) | 2016-07-06 |
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