KR101290896B1 - Corrosion resistant metal and method for modification of metal surfaces for corrosion resistance improvement using oxynitrocarburising process - Google Patents
Corrosion resistant metal and method for modification of metal surfaces for corrosion resistance improvement using oxynitrocarburising process Download PDFInfo
- Publication number
- KR101290896B1 KR101290896B1 KR1020110104641A KR20110104641A KR101290896B1 KR 101290896 B1 KR101290896 B1 KR 101290896B1 KR 1020110104641 A KR1020110104641 A KR 1020110104641A KR 20110104641 A KR20110104641 A KR 20110104641A KR 101290896 B1 KR101290896 B1 KR 101290896B1
- Authority
- KR
- South Korea
- Prior art keywords
- sulfate
- metal surface
- acid
- sulfide
- nitriding
- 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.)
- Active
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 77
- 239000002184 metal Substances 0.000 title claims abstract description 77
- 238000005260 corrosion Methods 0.000 title claims abstract description 39
- 230000007797 corrosion Effects 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 36
- 230000004048 modification Effects 0.000 title 1
- 238000012986 modification Methods 0.000 title 1
- 238000005121 nitriding Methods 0.000 claims abstract description 39
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007864 aqueous solution Substances 0.000 claims abstract description 32
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 32
- 239000011593 sulfur Substances 0.000 claims abstract description 32
- 230000003647 oxidation Effects 0.000 claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- 238000002715 modification method Methods 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000004767 nitrides Chemical class 0.000 claims abstract description 10
- 238000003958 fumigation Methods 0.000 claims abstract description 8
- 238000009792 diffusion process Methods 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 12
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 11
- QXKXDIKCIPXUPL-UHFFFAOYSA-N sulfanylidenemercury Chemical compound [Hg]=S QXKXDIKCIPXUPL-UHFFFAOYSA-N 0.000 claims description 11
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 8
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 8
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 8
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 8
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 5
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 4
- SQDAZGGFXASXDW-UHFFFAOYSA-N 5-bromo-2-(trifluoromethoxy)pyridine Chemical compound FC(F)(F)OC1=CC=C(Br)C=N1 SQDAZGGFXASXDW-UHFFFAOYSA-N 0.000 claims description 4
- JDLKFOPOAOFWQN-VIFPVBQESA-N Allicin Natural products C=CCS[S@](=O)CC=C JDLKFOPOAOFWQN-VIFPVBQESA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 229920001287 Chondroitin sulfate Polymers 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 4
- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical compound NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 claims description 4
- JDLKFOPOAOFWQN-UHFFFAOYSA-N allicin Chemical compound C=CCSS(=O)CC=C JDLKFOPOAOFWQN-UHFFFAOYSA-N 0.000 claims description 4
- 235000010081 allicin Nutrition 0.000 claims description 4
- COOGPNLGKIHLSK-UHFFFAOYSA-N aluminium sulfide Chemical compound [Al+3].[Al+3].[S-2].[S-2].[S-2] COOGPNLGKIHLSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- PJGXSCHDOCZUNR-UHFFFAOYSA-N azanium;2-sulfobenzoate Chemical compound [NH4+].OC(=O)C1=CC=CC=C1S([O-])(=O)=O PJGXSCHDOCZUNR-UHFFFAOYSA-N 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- YAECNLICDQSIKA-UHFFFAOYSA-L calcium;sulfanide Chemical compound [SH-].[SH-].[Ca+2] YAECNLICDQSIKA-UHFFFAOYSA-L 0.000 claims description 4
- 229940059329 chondroitin sulfate Drugs 0.000 claims description 4
- DBULDCSVZCUQIR-UHFFFAOYSA-N chromium(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Cr+3].[Cr+3] DBULDCSVZCUQIR-UHFFFAOYSA-N 0.000 claims description 4
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 4
- -1 copper sulfate anhydride Chemical class 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- ZHGASCUQXLPSDT-UHFFFAOYSA-N cyclohexanesulfonic acid Chemical compound OS(=O)(=O)C1CCCCC1 ZHGASCUQXLPSDT-UHFFFAOYSA-N 0.000 claims description 4
- 150000004662 dithiols Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- GNVXPFBEZCSHQZ-UHFFFAOYSA-N iron(2+);sulfide Chemical compound [S-2].[Fe+2] GNVXPFBEZCSHQZ-UHFFFAOYSA-N 0.000 claims description 4
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 4
- 235000011151 potassium sulphates Nutrition 0.000 claims description 4
- KHDSWONFYIAAPE-UHFFFAOYSA-N silicon sulfide Chemical compound S=[Si]=S KHDSWONFYIAAPE-UHFFFAOYSA-N 0.000 claims description 4
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 4
- 229940077386 sodium benzenesulfonate Drugs 0.000 claims description 4
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 4
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims description 4
- SMDQFHZIWNYSMR-UHFFFAOYSA-N sulfanylidenemagnesium Chemical compound S=[Mg] SMDQFHZIWNYSMR-UHFFFAOYSA-N 0.000 claims description 4
- 150000003555 thioacetals Chemical class 0.000 claims description 4
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- DNVLJEWNNDHELH-UHFFFAOYSA-N thiocyclam Chemical compound CN(C)C1CSSSC1 DNVLJEWNNDHELH-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 3
- 150000004056 anthraquinones Chemical class 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 150000004686 pentahydrates Chemical class 0.000 claims description 2
- 230000002265 prevention Effects 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000004018 waxing Methods 0.000 claims description 2
- WAKTWVHWRCNIKU-UHFFFAOYSA-N S(=O)(=O)(O)O.[AlH3] Chemical compound S(=O)(=O)(O)O.[AlH3] WAKTWVHWRCNIKU-UHFFFAOYSA-N 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 4
- 102200082816 rs34868397 Human genes 0.000 description 4
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 229910000967 As alloy Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910000677 High-carbon steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C23C8/34—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 more than one element being applied in more than one step
-
- 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
- C23C8/02—Pretreatment of the material to be coated
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
Abstract
본 발명은 산질화를 이용한 내식성 금속 및 내식성 향상을 위한 금속 표면 개질 방법에 관한 것으로, 보다 상세하게는 질화 단계 중 또는 질화 단계 후 순차적으로 금속 표면을 황(S)이 포함된 수용액 증기에 노출 및 훈증하여 산화 처리하는 산화 단계를 포함하는 내식성 향상을 위한 금속 표면 개질 방법 및 내식성 금속에 관한 것이다.
특히, 본 발명에 따른 금속 표면 개질 방법은 질화 처리와 동시에 또는 질화 처리 후 산화 처리 시 황(S) 성분을 포함한 물질을 추가로 투입함으로써 질화층 또는 확산층 상에 생성되는 산화층 내부의 기공층이 매우 많아지며 황(S)이 산소(O2), 철(Fe) 및 질소(N)의 결합력을 증가시켜 내식성이 증가되므로 습동성과 내마모성을 유지하면서 내식성까지 증가된 금속을 제공할 수 있다. The present invention relates to a corrosion-resistant metal using oxynitride and a method for modifying the metal surface for improving the corrosion resistance, and more particularly, the metal surface is sequentially exposed to sulfur (S) aqueous solution during or after nitriding step and The present invention relates to a metal surface modification method and a corrosion resistant metal for improving corrosion resistance including an oxidation step of fumigation.
In particular, in the metal surface modification method according to the present invention, the pore layer inside the oxide layer formed on the nitride layer or the diffusion layer is very much injected by additionally adding a substance containing sulfur (S) component simultaneously with the nitriding treatment or during the oxidation treatment. Since the sulfur (S) increases the bonding strength of oxygen (O 2 ), iron (Fe) and nitrogen (N) to increase the corrosion resistance it can provide an increased metal to corrosion resistance while maintaining slidability and wear resistance.
Description
본 발명은 산질화를 이용한 내식성 금속 및 내식성 향상을 위한 금속 표면 개질 방법에 관한 것으로, 보다 상세하게는 질화 단계 중 또는 질화 단계 후 순차적으로 금속 표면을 황(S)이 포함된 수용액 증기에 노출 및 훈증하여 산화 처리하는 산화 단계를 포함하는 내식성 향상을 위한 금속 표면 개질 방법에 관한 것이다. The present invention relates to a corrosion-resistant metal using oxynitride and a method for modifying the metal surface for improving the corrosion resistance, and more particularly, the metal surface is sequentially exposed to sulfur (S) aqueous solution during or after nitriding step and The present invention relates to a method of modifying a metal surface for improving corrosion resistance, including an oxidation step of fumigation and oxidation.
일반적으로 금속 표면의 내식성 증가를 위한 처리 방법으로는 페인팅, 도금, 코팅 및 산질화 처리가 이용되고 있다. In general, painting, plating, coating and oxynitride are used as treatment methods for increasing corrosion resistance of metal surfaces.
산질화 처리는 금속 표면에 질화 공정으로 질화층을 생성하고 상기 질화층 위에 산화층을 형성시켜 내마모성, 내습동성 및 내식성을 크게 부여하는 금속 표면 개질 방법으로서, 질화처리 방법과 산화처리 방법에 따라 여러 가지 방법이 제안되어 있다. Oxidative nitriding treatment is a metal surface modification method that creates a nitride layer on the metal surface by nitriding process and forms an oxide layer on the nitride layer to give abrasion resistance, slidability, and corrosion resistance. A method is proposed.
산질화의 대표적인 공법으로는 질소베이스법을 기초한 나이트로텍(NITROTEC)법, 염욕연질화 후 처리하는 QPQ 처리법 또는 OPO 처리법, 질화처리시 산화제를 투입하는 NN법 또는 로갈스키(Rogalski)법 등이 이용되고 있다. Representative methods of oxynitride include nitrotec method based on nitrogen base method, QPQ treatment or OPO treatment after salt bath nitriding, NN method to inject oxidant during nitriding or Rogalski method. It is used.
하지만, 전술한 산질화법은 합금강, 고탄소강에 내식성 증가에 효과가 있으나 저급강, 저탄소강에는 내식성 증가에 효과를 볼 수 없다는 단점이 있다. However, the above-mentioned oxynitride method has an effect of increasing the corrosion resistance of alloy steel and high carbon steel, but has a disadvantage of not having an effect of increasing the corrosion resistance of low grade steel and low carbon steel.
이에, 본 발명자들은 금속 표면의 내식성 향상을 위한 산질화 처리 시 질화 단계 중 또는 질화 단계 후 순차적으로 금속 표면을 황(S)이 포함된 수용액 증기에 노출 및 훈증하고 산화 처리하여 저급강, 저탄소강에서도 개선된 내식성 특성을 확인함으로써 본 발명을 완성하였다. Accordingly, the present inventors exposed and fumigated the metal surface to an aqueous solution vapor containing sulfur (S) during or after the nitriding step or the nitriding step in order to improve the corrosion resistance of the metal surface. The present invention was completed by confirming the improved corrosion resistance properties.
본 발명의 목적은 저급강, 저탄소강에 산질화를 처리하여 합금강과 동일하거나 우수한 내식성을 갖는 내식성 금속을 제공하는 데에 있다. An object of the present invention is to provide a corrosion resistant metal having the same or better corrosion resistance as alloy steel by treating oxynitride with low grade steel and low carbon steel.
본 발명의 다른 목적은 저급강, 저탄소강에 산질화를 처리하여 합금강과 동일하거나 우수한 내식성을 부여할 수 있도록 하는 금속 표면 개질 방법을 제공하는 데에 있다. Another object of the present invention is to provide a metal surface modification method for treating oxynitride on low grade steel and low carbon steel to give the same or better corrosion resistance as alloy steel.
상기 목적을 달성하기 위하여, 본 발명은 황(S)이 포함된 수용액을 0.1 내지 10 중량%의 함량으로 금속 표면에 처리하여 얻어진 질화층 및 산화층을 포함하는 것을 특징으로 하는 내식성 금속을 제공한다. In order to achieve the above object, the present invention provides a corrosion-resistant metal comprising a nitride layer and an oxide layer obtained by treating the surface of the metal with an aqueous solution containing sulfur (S) in an amount of 0.1 to 10% by weight.
상기 금속 표면은 표면세척, 예열 및 질화를 거쳐 처리되되, 상기 질화 중 또는 질화 후 순차적으로 금속 표면을 황(S)이 포함된 수용액 증기에 노출 및 훈증하여 산화 처리할 수 있다.The metal surface may be treated by surface cleaning, preheating, and nitriding, and the metal surface may be oxidized by sequentially exposing and fumigating the metal surface to an aqueous solution containing sulfur (S) during or after nitriding.
상기 황(S)이 포함된 수용액은 황산(H2SO4), 이산화황(SO2), 삼산화황(SO3), 아황산(H2SO3), 황산구리 무수물(CuSO4), 황산구리(Ⅱ) 오수화물(CuSO4·5H2O), 황산납(PbSO4), 황산바륨(BaSO4), 황산나트륨(Na2SO4), 황산소수나트륨(NaHSO4), 황산아연(ZnSO4), 황산알루미늄(Al2(SO4)3), 황산암모늄((NH4)2SO4)), 황산은(Ag2SO4), 황산칼슘(CaSO4), 황산마그네슘(MgSO4), 황산크로뮴(Cr2(SO4)3), 황산포타슘(K2SO4), 황화구리(CuS), 황화마그네슘(MgS), 황화수소(H2S), 황화수은(II)(HgS), 황화철(FeS), 황화카드늄(CdS), 메테인설폰산(CH3SO3H), 아황산수소소듐(NaHSO3), 사이클로헥세인설폰산((CH2)6SO2), 벤젠설폰산(C6H5SO3H), 이황화탄소(CS2), 황화수소나트륨(NaHS), 벤젠설폰산나트륨(C6H5SO3Na), 황화수고칼슘(Ca(SH)2), 황화알루미늄(Al2S3), 황화크로뮴(Cr2S3), 황화규소(SiS2), 싸이오페놀(thiophenol), 다이싸이올 (dithiol), 메테인싸이올(CH4S), 싸이오아세탈(thioacetal), 싸이오사이클램(thiocyclam), 싸이오아세트아마이드, 싸이오카르밤산암모늄, 설포벤조산아마이드, 알리신(allicin), 황산콘드로이친(chondroitin sulfate), 나프탈렌설폰산(naphthalenesulfonic acid), 벤젠설폰산, 나프톨설폰산(naphtholsulfonic acid), 톨루엔설폰산 및 안트라퀴논설폰산으로 이루어진 군에서 선택된 어느 하나의 수용액일 수 있지만, 이에 한정되는 것은 아니며 황을 포함하는 어떠한 물질의 수용액도 사용될 수 있다.The aqueous solution containing sulfur (S) is sulfuric acid (H 2 SO 4 ), sulfur dioxide (SO 2 ), sulfur trioxide (SO 3 ), sulfurous acid (H 2 SO 3 ), copper sulfate anhydride (CuSO 4 ), copper sulfate (II) cargo (CuSO 4 · 5H 2 O) , lead sulfate (PbSO 4), barium sulfate (BaSO 4), sodium sulfate (Na 2 SO 4), sulfuric acid, a small number of sodium (NaHSO 4), zinc sulfate (ZnSO 4), aluminum sulfate ( Al 2 (SO 4 ) 3 ), ammonium sulfate ((NH 4 ) 2 SO 4 )), silver sulfate (Ag 2 SO 4 ), calcium sulfate (CaSO 4 ), magnesium sulfate (MgSO 4 ), Chromium sulfate (Cr 2 (SO 4 ) 3 ), potassium sulfate (K 2 SO 4 ), copper sulfide (CuS), magnesium sulfide (MgS), hydrogen sulfide (H 2 S), mercury sulfide (II) (HgS), iron sulfide (FeS), cadmium sulfide (CdS), methanesulfonic acid (CH 3 SO 3 H), sodium hydrogen sulfite (NaHSO 3 ), cyclohexanesulfonic acid ((CH 2 ) 6 SO 2 ), benzenesulfonic acid (C 6 H 5 SO 3 H), carbon disulfide (CS 2 ), sodium hydrogen sulfide (NaHS), sodium benzenesulfonate (C 6 H 5 SO 3 Na), calcium hydrosulfide (Ca (SH) 2 ), aluminum sulfide (Al 2 S 3 ), chromium sulfide (Cr 2 S 3 ), silicon sulfide (SiS 2 ), thiophenol, dithiol, methanethiol (CH 4 S), thioacetal , Thiocyclam, thioacetamide, thiocarbamate, ammonium sulfobenzoic acid, allicin, chondroitin sulfate, naphthalenesulfonic acid, benzenesulfonic acid, naphtholsul Naphtholsulfonic acid, toluenesulfonic acid and anthraquinone May be any one of an aqueous solution selected from the group consisting of acid, not limited to this can also be used in any aqueous solution of a substance containing sulfur.
또한, 본 발명은 표면세척 단계, 예열 단계 및 질화 단계를 포함하는 내식성 향상을 위한 금속 표면 개질 방법에 있어서, 상기 질화 단계 중 또는 질화 단계 후 순차적으로 금속 표면을 황(S)이 포함된 수용액 증기에 노출 및 훈증하여 산화 처리하는 산화 단계를 포함하는 것을 특징으로 하는 내식성 향상을 위한 금속 표면 개질 방법을 제공한다.In addition, the present invention in the metal surface modification method for improving the corrosion resistance including the surface cleaning step, preheating step and nitriding step, the aqueous solution vapor containing sulfur (S) during the nitriding step or after the nitriding step sequentially It provides a metal surface modification method for improving the corrosion resistance, characterized in that it comprises an oxidation step of the oxidation treatment by exposure and fumigation.
본 발명의 일 실시예로는, 금속표면에 이물질 및 유분을 제거하는 표면세척 단계; 상기 표면세척 단계를 수행한 금속 표면을 가열하여 예열하는 예열 단계; 및 상기 예열단계를 통해 예열된 금속 표면에 질화층 및 확산층 중 적어도 어느 하나가 형성되도록 하면서 동시에 금속 표면을 황(S)이 포함된 수용액 증기에 노출 및 훈증하여 산화 처리하는 산화 단계를 포함하는 것을 특징으로 하는 내식성 향상을 위한 금속 표면 개질 방법을 제공한다.In one embodiment of the present invention, the surface washing step of removing foreign matter and oil on the metal surface; A preheating step of heating and preheating the metal surface on which the surface cleaning step is performed; And an oxidation step in which at least one of a nitride layer and a diffusion layer is formed on the metal surface preheated through the preheating step, and at the same time, the metal surface is oxidized by exposing and fumigation to an aqueous vapor containing sulfur (S). A metal surface modification method for improving corrosion resistance is provided.
본 발명의 다른 일 실시예로는, 금속표면에 이물질 및 유분을 제거하는 표면세척 단계; 상기 표면세척 단계를 수행한 금속 표면을 가열하여 예열하는 예열 단계; 상기 예열단계를 통해 예열된 금속 표면에 질화층 및 확산층 중 적어도 어느 하나가 형성되도록 하는 질화 단계; 및 상기 질화 단계에서 처리된 금속 표면을 황(S)이 포함된 수용액 증기에 노출 및 훈증하여 산화 처리하는 산화 단계를 포함하는 것을 특징으로 하는 내식성 향상을 위한 금속 표면 개질 방법을 제공한다.Another embodiment of the present invention, the surface cleaning step of removing foreign matter and oil on the metal surface; A preheating step of heating and preheating the metal surface on which the surface cleaning step is performed; A nitriding step of forming at least one of a nitride layer and a diffusion layer on the metal surface preheated through the preheating step; And an oxidation step of oxidizing and exposing the metal surface treated in the nitriding step to an aqueous solution vapor containing sulfur (S), and fumigation.
본 발명에서 상기 질화 단계는 암모니아(NH3) 가스만 질화로에 투입하여 질화 과정을 수행하는 가스질화법; 또는 질소(N), 이산화탄소(CO2) 및 암모니아(NH3)를 질화로에 투입하여 질화 과정을 수행하는 가스연질화법 중에서 선택된 어느 하나의 방법을 이용하여 수행할 수 있다.In the present invention, the nitriding step includes a gas nitriding method in which only ammonia (NH 3 ) gas is added to the nitriding furnace to carry out a nitriding process; Alternatively, nitrogen (N), carbon dioxide (CO 2 ), and ammonia (NH 3 ) may be performed using any one method selected from a gas soft nitriding method in which a nitriding process is performed.
본 발명에서 상기 산화단계는 로 내부에 상기 금속 모재를 장입하고, 내부 온도가 350℃ 내지 600℃의 범위가 되도록 하는 승온하는 장입 및 승온 단계; 및 상기 장입 및 승온 단계의 최종 온도를 그대로 유지하면서 황(S)이 포함된 수용액 증기를 투입하고 처리하는 황(S) 수용액 증기 투입 단계를 포함할 수 있다.In the present invention, the oxidation step is charged and heated step of charging the metal base material in the furnace, the internal temperature is 350 ℃ to 600 ℃ range; And a sulfur (S) aqueous solution steam input step of inputting and treating an aqueous solution vapor containing sulfur (S) while maintaining the final temperature of the charging and temperature raising step.
보다 상세하게는, 상기 산화단계는 로 내부에 상기 금속 모재를 장입하고, 내부 온도가 350℃ 내지 600℃의 범위가 되도록 하는 승온하는 장입 및 승온 단계; 및 상기 장입 및 승온 단계의 최종 온도를 그대로 유지하면서 황(S)이 포함된 수용액 증기 0.1 내지 10 중량%를 투입하고 1 내지 60분 동안 처리하는 황(S) 수용액 증기 투입 단계를 포함할 수 있다. More specifically, the oxidation step may be charged and heated step of charging the metal base material in the furnace, the internal temperature is 350 ℃ to 600 ℃ range; And while maintaining the final temperature of the charging and the step of raising the temperature may include a sulfur (S) aqueous solution steam input step of adding 0.1 to 10% by weight of an aqueous solution steam containing sulfur (S) and processing for 1 to 60 minutes. .
상기 산화 단계에서 내부 온도가 상기 범위를 벗어나면 Fe2O3가 생성되어 적청화되고 제품의 색상이 변화되는 문제가 야기될 수 있으며, 황(S)이 포함된 수용액 증기의 함유량이 상기 범위를 벗어나면 질화층과 산화층이 견고하게 접착되지 못하는 문제가 야기될 수 있고, 황(S)이 포함된 수용액 증기의 처리 시간이 상기 범위를 벗어나면 박리현상, 황산화 현상 및 수용액의 기화가 원활하지 못한 문제가 야기될 수 있다.When the internal temperature is out of the range in the oxidation step, Fe 2 O 3 may be generated to cause red blue crystals and to change the color of the product, and the content of the aqueous vapor containing sulfur (S) may be in the above range. If this occurs, the nitride layer and the oxide layer may not be firmly adhered to each other. If the treatment time of the aqueous solution vapor containing sulfur (S) is out of the above range, the peeling phenomenon, the sulfation phenomenon, and the vaporization of the aqueous solution may not be smooth. Unsuccessful problems may arise.
본 발명에서 상기 산화 단계에 투입되는 황(S) 수용액은 황산(H2SO4), 이산화황(SO2), 삼산화황(SO3), 아황산(H2SO3), 황산구리 무수물(CuSO4), 황산구리(Ⅱ) 오수화물(CuSO4·5H2O), 황산납(PbSO4), 황산바륨(BaSO4), 황산나트륨(Na2SO4), 황산소수나트륨(NaHSO4), 황산아연(ZnSO4), 황산알루미늄(Al2(SO4)3), 황산암모늄((NH4)2SO4)), 황산은(Ag2SO4), 황산칼슘(CaSO4), 황산마그네슘(MgSO4), 황산크로뮴(Cr2(SO4)3), 황산포타슘(K2SO4), 황화구리(CuS), 황화마그네슘(MgS), 황화수소(H2S), 황화수은(II)(HgS), 황화철(FeS), 황화카드늄(CdS), 메테인설폰산(CH3SO3H), 아황산수소소듐(NaHSO3), 사이클로헥세인설폰산((CH2)6SO2), 벤젠설폰산(C6H5SO3H), 이황화탄소(CS2), 황화수소나트륨(NaHS), 벤젠설폰산나트륨(C6H5SO3Na), 황화수고칼슘(Ca(SH)2), 황화알루미늄(Al2S3), 황화크로뮴(Cr2S3), 황화규소(SiS2), 싸이오페놀(thiophenol), 다이싸이올 (dithiol), 메테인싸이올(CH4S), 싸이오아세탈(thioacetal), 싸이오사이클램(thiocyclam), 싸이오아세트아마이드, 싸이오카르밤산암모늄, 설포벤조산아마이드, 알리신(allicin), 황산콘드로이친(chondroitin sulfate), 나프탈렌설폰산(naphthalenesulfonic acid), 벤젠설폰산, 나프톨설폰산(naphtholsulfonic acid), 톨루엔설폰산 또는 안트라퀴논설폰산에서 선택된 어느 하나의 수용액일 수 있지만, 이에 한정되는 것은 아니며 황을 포함하는 어떠한 물질의 수용액도 사용될 수 있다.In the present invention, the sulfur (S) aqueous solution introduced into the oxidation step is sulfuric acid (H 2 SO 4 ), sulfur dioxide (SO 2 ), sulfur trioxide (SO 3 ), sulfurous acid (H 2 SO 3 ), copper sulfate anhydride (CuSO 4 ), Copper sulfate (II) pentahydrate (CuSO 4 · 5H 2 O), lead sulfate (PbSO 4 ), barium sulfate (BaSO 4 ), sodium sulfate (Na 2 SO 4 ), sodium hydrogen sulfate (NaHSO 4 ), zinc sulfate (ZnSO 4 ), Aluminum sulfate (Al 2 (SO 4 ) 3 ), ammonium sulfate ((NH 4 ) 2 SO 4 )), silver sulfate (Ag 2 SO 4 ), calcium sulfate (CaSO 4 ), magnesium sulfate (MgSO 4 ), Chromium sulfate (Cr 2 (SO 4 ) 3 ), potassium sulfate (K 2 SO 4 ), copper sulfide (CuS), magnesium sulfide (MgS), hydrogen sulfide (H 2 S), mercury sulfide (II) (HgS), iron sulfide (FeS), cadmium sulfide (CdS), methanesulfonic acid (CH 3 SO 3 H), sodium hydrogen sulfite (NaHSO 3 ), cyclohexanesulfonic acid ((CH 2 ) 6 SO 2 ), benzenesulfonic acid (C 6 H 5 SO 3 H), carbon disulfide (CS 2 ), sodium hydrogen sulfide (NaHS), sodium benzenesulfonate (C 6 H 5 SO 3 Na), calcium hydrosulfide (Ca (SH) 2 ), aluminum sulfide (Al 2 S 3 ), chromium sulfide (Cr 2 S 3 ), silicon sulfide (SiS 2 ), thiophenol, dithiol, methanethiol (CH 4 S), thioacetal , Thiocyclam, thioacetamide, thiocarbamate, ammonium sulfobenzoic acid, allicin, chondroitin sulfate, naphthalenesulfonic acid, benzenesulfonic acid, naphtholsul Naphtholsulfonic acid, toluenesulfonic acid or anthraqui It may be any one selected from aqueous solutions of the acid, not limited to this may also be used an aqueous solution of any material which contains sulfur.
본 발명에 따른 금속 표면 개질 방법은 상기 산화 단계 후, 방청, 실링(Sealing), 왁싱(Waxing) 및 코팅(Coating)으로 이루어진 군에서 선택된 어느 하나 이상의 단계를 더 포함할 수 있다.The metal surface modification method according to the present invention may further include any one or more steps selected from the group consisting of rust prevention, sealing, waxing, and coating after the oxidation step.
또한, 본 발명은 상기 금속 표면 개질 방법을 통해 금속 표면이 개질된 것을 특징으로 하는 내식성 금속을 제공할 수 있다.In addition, the present invention can provide a corrosion-resistant metal, characterized in that the metal surface is modified through the metal surface modification method.
본 발명에 따른 내식성 금속 및 금속 표면 개질 방법은 질화 처리와 동시에 또는 질환 처리 후 산화 처리 시 황(S) 성분을 포함한 물질을 추가로 투입함으로써 질화층 또는 확산층 상에 생성되는 산화층 내부의 기공층이 매우 많아지며 황(S)이 산소(O2), 철(Fe) 및 질소(N)의 결합력을 증가시켜 내식성이 증가되므로 습동성과 내마모성을 유지하면서 내식성까지 증가되는 효과가 있다. Corrosion-resistant metals and metal surface modification method according to the present invention is a pore layer inside the oxide layer formed on the nitride layer or the diffusion layer by adding a substance containing sulfur (S) component at the same time as the nitriding treatment or during the oxidation treatment after disease treatment Since the sulfur (S) increases the bonding strength of oxygen (O 2 ), iron (Fe) and nitrogen (N) to increase the corrosion resistance, there is an effect to increase the corrosion resistance while maintaining slidability and wear resistance.
도 1은 본 발명의 일실시예에 따른 금속 표면 개질 방법을 나타낸 것이고,
도 2는 본 발명의 다른 일실시예에 따른 금속 표면 개질 방법을 나타낸 것이다.1 shows a metal surface modification method according to an embodiment of the present invention,
Figure 2 shows a metal surface modification method according to another embodiment of the present invention.
본 발명은 질화 단계 중 또는 질화 단계 후 순차적으로 금속 표면을 황(S)이 포함된 수용액 증기에 노출 및 훈증하여 산화 처리하는 산화 단계를 포함하는 내식성 향상을 위한 금속 표면 개질 방법에 관한 것으로, 하기 실시예를 통해 본 발명을 보다 상세하게 설명한다. 다만, 이러한 실시예에 의해 본 발명이 한정되는 것은 아니다.
The present invention relates to a metal surface modification method for improving corrosion resistance, comprising an oxidation step of oxidizing and exposing and fusing a metal surface to an aqueous solution vapor containing sulfur (S) sequentially during or after nitriding. The present invention will be described in more detail with reference to Examples. However, the present invention is not limited by these examples.
<실시예 1> 본 발명에 따른 산질화를 이용한 금속 표면 처리Example 1 Metal Surface Treatment Using Oxidation according to the Present Invention
JIS SPCC, JIS SAPH440, S45C 재질의 시편을 JIG에 배열하여 T.E.C.증기로 약 80~90도에서 1시간 먼저 표면 세척한 후, 하기 표 1과 같은 공정 조건 하에서 금속 표면을 개질하였다.The specimens made of JIS SPCC, JIS SAPH440, and S45C were arranged in JIG, and then surface-washed at about 80 to 90 degrees with T.E.C. steam for 1 hour, and then the metal surface was modified under the process conditions shown in Table 1 below.
<실시예 2> 본 발명에 따른 산질화를 이용한 금속 표면 처리Example 2 Metal Surface Treatment Using Oxidation according to the Present Invention
JIS SPCC, JIS SAPH440, S45C 재질의 시편을 JIG에 배열하여 T.E.C.증기로 약 80~90도에서 1시간 먼저 표면 세척한 후, 하기 표 2와 같은 공정 조건 하에서 금속 표면을 개질하였다.The specimens made of JIS SPCC, JIS SAPH440, and S45C were arranged in JIG to be first surface-washed at about 80 to 90 degrees with T.E.C. steam for 1 hour, and then the metal surface was modified under the process conditions shown in Table 2 below.
<비교예 1> 일반 산질화를 이용한 금속 표면 처리 Comparative Example 1 Metal Surface Treatment Using General Oxidation
JIS SPCC, JIS SAPH440, S45C 재질의 시편을 JIG에 배열하여 T.E.C.증기로 약 80~90도에서 1시간 먼저 표면 세척한 후, 하기 표 3과 같은 공정 조건 하에서 금속 표면을 개질하였다.The specimens made of JIS SPCC, JIS SAPH440, and S45C were arranged in JIG, and then surface-washed at about 80 to 90 degrees with T.E.C. steam for 1 hour, and then the metal surface was modified under the process conditions shown in Table 3 below.
<< 실험예Experimental Example 1> 내식성 평가 1> corrosion resistance evaluation
염수분무시험(KSM2109)을 이용하여 내식성 시험을 수행한 결과, 하기 표 4와 같이 실시예와 같이 표면 처리된 금속이 비교예인 일반 산질화 공정을 통해 표면 처리된 금속에 비해 내식성이 크게 향상되는 것을 확인할 수 있었다. As a result of performing a corrosion resistance test using the salt spray test (KSM2109), as shown in Table 4, the surface-treated metal as shown in Example 4 is significantly improved in the corrosion resistance compared to the surface-treated metal through the general oxynitride process as a comparative example I could confirm it.
이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는 바, 당업계의 통상의 지식을 가진 자에게 있어서, 이러한 구체적 기술은 단지 바람직한 실시양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다. While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. something to do. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.
Claims (11)
상기 황(S)이 포함된 수용액은 황산(H2SO4), 이산화황(SO2), 삼산화황(SO3), 아황산(H2SO3), 황산구리 무수물(CuSO4), 황산구리(Ⅱ) 오수화물(CuSO4·5H2O), 황산납(PbSO4), 황산바륨(BaSO4), 황산나트륨(Na2SO4), 황산소수나트륨(NaHSO4), 황산아연(ZnSO4), 황산알루미늄(Al2(SO4)3), 황산암모늄((NH4)2SO4)), 황산은(Ag2SO4), 황산칼슘(CaSO4), 황산마그네슘(MgSO4), 황산크로뮴(Cr2(SO4)3), 황산포타슘(K2SO4), 황화구리(CuS), 황화마그네슘(MgS), 황화수소(H2S), 황화수은(II)(HgS), 황화철(FeS), 황화카드늄(CdS), 메테인설폰산(CH3SO3H), 아황산수소소듐(NaHSO3), 사이클로헥세인설폰산((CH2)6SO2), 벤젠설폰산(C6H5SO3H), 이황화탄소(CS2), 황화수소나트륨(NaHS), 벤젠설폰산나트륨(C6H5SO3Na), 황화수고칼슘(Ca(SH)2), 황화알루미늄(Al2S3), 황화크로뮴(Cr2S3), 황화규소(SiS2), 싸이오페놀(thiophenol), 다이싸이올 (dithiol), 메테인싸이올(CH4S), 싸이오아세탈(thioacetal), 싸이오사이클램(thiocyclam), 싸이오아세트아마이드, 싸이오카르밤산암모늄, 설포벤조산아마이드, 알리신(allicin), 황산콘드로이친(chondroitin sulfate), 나프탈렌설폰산(naphthalenesulfonic acid), 벤젠설폰산, 나프톨설폰산(naphtholsulfonic acid), 톨루엔설폰산 및 안트라퀴논설폰산으로 이루어진 군에서 선택된 어느 하나의 수용액인 것을 특징으로 하는 내식성 금속.The method according to claim 2,
The aqueous solution containing sulfur (S) is sulfuric acid (H 2 SO 4 ), sulfur dioxide (SO 2 ), sulfur trioxide (SO 3 ), sulfurous acid (H 2 SO 3 ), copper sulfate anhydride (CuSO 4 ), copper sulfate (II) cargo (CuSO 4 · 5H 2 O) , lead sulfate (PbSO 4), barium sulfate (BaSO 4), sodium sulfate (Na 2 SO 4), sulfuric acid, a small number of sodium (NaHSO 4), zinc sulfate (ZnSO 4), aluminum sulfate ( Al 2 (SO 4 ) 3 ), ammonium sulfate ((NH 4 ) 2 SO 4 )), silver sulfate (Ag 2 SO 4 ), calcium sulfate (CaSO 4 ), magnesium sulfate (MgSO 4 ), Chromium sulfate (Cr 2 (SO 4 ) 3 ), potassium sulfate (K 2 SO 4 ), copper sulfide (CuS), magnesium sulfide (MgS), hydrogen sulfide (H 2 S), mercury sulfide (II) (HgS), iron sulfide (FeS), cadmium sulfide (CdS), methanesulfonic acid (CH 3 SO 3 H), sodium hydrogen sulfite (NaHSO 3 ), cyclohexanesulfonic acid ((CH 2 ) 6 SO 2 ), benzenesulfonic acid (C 6 H 5 SO 3 H), carbon disulfide (CS 2 ), sodium hydrogen sulfide (NaHS), sodium benzenesulfonate (C 6 H 5 SO 3 Na), calcium hydrosulfide (Ca (SH) 2 ), aluminum sulfide (Al 2 S 3 ), chromium sulfide (Cr 2 S 3 ), silicon sulfide (SiS 2 ), thiophenol, dithiol, methanethiol (CH 4 S), thioacetal , Thiocyclam, thioacetamide, thiocarbamate, ammonium sulfobenzoic acid, allicin, chondroitin sulfate, naphthalenesulfonic acid, benzenesulfonic acid, naphtholsul Naphtholsulfonic acid, toluenesulfonic acid and anthraquinone Corrosion-resistant metal as one characterized in that the aqueous solution of an acid selected from the group consisting of.
금속표면에 이물질 및 유분을 제거하는 표면세척 단계;
상기 표면세척 단계를 수행한 금속 표면을 가열하여 예열하는 예열 단계; 및
상기 예열단계를 통해 예열된 금속 표면에 질화층 및 확산층 중 적어도 어느 하나가 형성되도록 하면서 동시에 금속 표면을 황(S)이 포함된 수용액 증기에 노출 및 훈증하여 산화 처리하는 산화 단계
를 포함하는 것을 특징으로 하는 내식성 향상을 위한 금속 표면 개질 방법.The method of claim 4,
A surface washing step of removing foreign substances and oil from the metal surface;
A preheating step of heating and preheating the metal surface on which the surface cleaning step is performed; And
At least one of a nitride layer and a diffusion layer is formed on the preheated metal surface through the preheating step, and an oxidation step of subjecting the metal surface to an aqueous solution vapor containing sulfur (S) and fumigation to oxidize it.
Metal surface modification method for improving the corrosion resistance comprising a.
금속표면에 이물질 및 유분을 제거하는 표면세척 단계;
상기 표면세척 단계를 수행한 금속 표면을 가열하여 예열하는 예열 단계;
상기 예열단계를 통해 예열된 금속 표면에 질화층 및 확산층 중 적어도 어느 하나가 형성되도록 하는 질화 단계; 및
상기 질화 단계에서 처리된 금속 표면을 황(S)이 포함된 수용액 증기에 노출 및 훈증하여 산화 처리하는 산화 단계
를 포함하는 것을 특징으로 하는 내식성 향상을 위한 금속 표면 개질 방법.The method of claim 4,
A surface washing step of removing foreign substances and oil from the metal surface;
A preheating step of heating and preheating the metal surface on which the surface cleaning step is performed;
A nitriding step of forming at least one of a nitride layer and a diffusion layer on the preheated metal surface through the preheating step; And
An oxidation step of subjecting the metal surface treated in the nitriding step to an oxidation process by exposing and fumigation to an aqueous solution vapor containing sulfur (S).
Metal surface modification method for improving the corrosion resistance comprising a.
상기 질화 단계는 암모니아(NH3) 가스만 질화로에 투입하여 질화 과정을 수행하는 가스질화법; 또는 질소(N), 이산화탄소(CO2) 및 암모니아(NH3)를 질화로에 투입하여 질화 과정을 수행하는 가스연질화법 중에서 선택된 어느 하나의 방법을 이용하여 수행할 수 있는 것을 특징으로 하는 내식성 향상을 위한 금속 표면 개질 방법.The method of claim 4,
The nitriding step includes a gas nitriding method in which only ammonia (NH 3 ) gas is added to the nitriding furnace to perform nitriding process; Alternatively, nitrogen (N), carbon dioxide (CO 2 ), and ammonia (NH 3 ) may be performed by using any one method selected from a gas soft nitriding method in which a nitriding process is carried out. Metal surface modification method.
상기 산화단계는 로 내부에 상기 금속 모재를 장입하고, 내부 온도가 350℃ 내지 600℃의 범위가 되도록 하는 승온하는 장입 및 승온 단계; 및 상기 장입 및 승온 단계의 최종 온도를 그대로 유지하면서 황(S)이 포함된 수용액 증기를 투입하고 처리하는 황(S) 수용액 증기 투입 단계를 포함하는 것을 특징으로 하는 내식성 향상을 위한 금속 표면 개질 방법.The method of claim 4,
The oxidation step is charged and heated step of charging the metal base material in the furnace, the temperature rising so that the internal temperature is in the range of 350 ℃ to 600 ℃; And a sulfur (S) aqueous solution steam input step of injecting and treating an aqueous solution vapor containing sulfur (S) while maintaining the final temperature of the charging and temperature raising step as it is. .
상기 산화 단계에 투입되는 황(S) 수용액은 황산(H2SO4), 이산화황(SO2), 삼산화황(SO3), 아황산(H2SO3), 황산구리 무수물(CuSO4), 황산구리(Ⅱ) 오수화물(CuSO4·5H2O), 황산납(PbSO4), 황산바륨(BaSO4), 황산나트륨(Na2SO4), 황산소수나트륨(NaHSO4), 황산아연(ZnSO4), 황산알루미늄(Al2(SO4)3), 황산암모늄((NH4)2SO4)), 황산은(Ag2SO4), 황산칼슘(CaSO4), 황산마그네슘(MgSO4), 황산크로뮴(Cr2(SO4)3), 황산포타슘(K2SO4), 황화구리(CuS), 황화마그네슘(MgS), 황화수소(H2S), 황화수은(II)(HgS), 황화철(FeS), 황화카드늄(CdS), 메테인설폰산(CH3SO3H), 아황산수소소듐(NaHSO3), 사이클로헥세인설폰산((CH2)6SO2), 벤젠설폰산(C6H5SO3H), 이황화탄소(CS2), 황화수소나트륨(NaHS), 벤젠설폰산나트륨(C6H5SO3Na), 황화수고칼슘(Ca(SH)2), 황화알루미늄(Al2S3), 황화크로뮴(Cr2S3), 황화규소(SiS2), 싸이오페놀(thiophenol), 다이싸이올 (dithiol), 메테인싸이올(CH4S), 싸이오아세탈(thioacetal), 싸이오사이클램(thiocyclam), 싸이오아세트아마이드, 싸이오카르밤산암모늄, 설포벤조산아마이드, 알리신(allicin), 황산콘드로이친(chondroitin sulfate), 나프탈렌설폰산(naphthalenesulfonic acid), 벤젠설폰산, 나프톨설폰산(naphtholsulfonic acid), 톨루엔설폰산 및 안트라퀴논설폰산으로 이루어진 군에서 선택된 어느 하나의 수용액인 것을 특징으로 하는 내식성 향상을 위한 금속 표면 개질 방법.The method of claim 4,
Sulfur (S) aqueous solution added to the oxidation step is sulfuric acid (H 2 SO 4 ), sulfur dioxide (SO 2 ), sulfur trioxide (SO 3 ), sulfurous acid (H 2 SO 3 ), copper sulfate anhydride (CuSO 4 ), copper sulfate (II ) pentahydrate (CuSO 4 · 5H 2 O) , lead sulfate (PbSO 4), barium sulfate (BaSO 4), sodium sulfate (Na 2 SO 4), sulfuric acid, a small number of sodium (NaHSO 4), zinc sulfate (ZnSO 4), sulfuric acid Aluminum (Al 2 (SO 4 ) 3 ), ammonium sulfate ((NH 4 ) 2 SO 4 )), silver sulfate (Ag 2 SO 4 ), calcium sulfate (CaSO 4 ), magnesium sulfate (MgSO 4 ), Chromium sulfate (Cr 2 (SO 4 ) 3 ), potassium sulfate (K 2 SO 4 ), copper sulfide (CuS), magnesium sulfide (MgS), hydrogen sulfide (H 2 S), mercury sulfide (II) (HgS), iron sulfide (FeS), cadmium sulfide (CdS), methanesulfonic acid (CH 3 SO 3 H), sodium hydrogen sulfite (NaHSO 3 ), cyclohexanesulfonic acid ((CH 2 ) 6 SO 2 ), benzenesulfonic acid (C 6 H 5 SO 3 H), carbon disulfide (CS 2 ), sodium hydrogen sulfide (NaHS), sodium benzenesulfonate (C 6 H 5 SO 3 Na), calcium hydrosulfide (Ca (SH) 2 ), aluminum sulfide (Al 2 S 3 ), chromium sulfide (Cr 2 S 3 ), silicon sulfide (SiS 2 ), thiophenol, dithiol, methanethiol (CH 4 S), thioacetal , Thiocyclam, thioacetamide, thiocarbamate, ammonium sulfobenzoic acid, allicin, chondroitin sulfate, naphthalenesulfonic acid, benzenesulfonic acid, naphtholsul Naphtholsulfonic acid, toluenesulfonic acid and anthraquinone Metal surface modification method for improving the corrosion resistance, characterized in that any one selected from the group consisting of an aqueous solution of acid.
상기 금속 표면 개질 방법은 산화 단계 후, 방청, 실링(Sealing), 왁싱(Waxing) 및 코팅(Coating)으로 이루어진 군에서 선택된 어느 하나 이상의 단계를 더 포함하는 것을 특징으로 하는 내식성 향상을 위한 금속 표면 개질 방법.The method of claim 4,
The metal surface modification method further includes any one or more steps selected from the group consisting of rust prevention, sealing, waxing, and coating after the oxidation step. Way.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110104641A KR101290896B1 (en) | 2011-10-13 | 2011-10-13 | Corrosion resistant metal and method for modification of metal surfaces for corrosion resistance improvement using oxynitrocarburising process |
| PCT/KR2012/003438 WO2013054997A1 (en) | 2011-10-13 | 2012-05-02 | Corrosion resistant metal and metal-surface modification method for improving corrosion resistance using oxynitriding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110104641A KR101290896B1 (en) | 2011-10-13 | 2011-10-13 | Corrosion resistant metal and method for modification of metal surfaces for corrosion resistance improvement using oxynitrocarburising process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20130039947A KR20130039947A (en) | 2013-04-23 |
| KR101290896B1 true KR101290896B1 (en) | 2013-07-29 |
Family
ID=48082027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020110104641A Active KR101290896B1 (en) | 2011-10-13 | 2011-10-13 | Corrosion resistant metal and method for modification of metal surfaces for corrosion resistance improvement using oxynitrocarburising process |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR101290896B1 (en) |
| WO (1) | WO2013054997A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102112796B1 (en) * | 2019-12-11 | 2020-05-19 | 신기산업 주식회사 | Method of Mold Part Surface Oxidation Heat Treatment |
| KR20200143112A (en) | 2019-06-14 | 2020-12-23 | 현대자동차주식회사 | Ceramic paint composition and brake disc plate for vehicle comprising the same |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9673042B2 (en) | 2015-09-01 | 2017-06-06 | Applied Materials, Inc. | Methods and apparatus for in-situ cleaning of copper surfaces and deposition and removal of self-assembled monolayers |
| CN106000656B (en) * | 2016-05-31 | 2018-10-16 | 北京矿冶研究总院 | Copper-lead inhibitor and application thereof |
| CN107502852B (en) * | 2017-08-18 | 2019-08-13 | 无锡市奕珺金属改性技术有限公司 | Component surface processing equipment and component surface treatment process |
| CN114293135B (en) * | 2021-05-06 | 2023-12-08 | 扬州大学 | Oxynitriding composite strengthening treatment process for gas surface of piston rod of automobile shock absorber |
| CN113897579A (en) * | 2021-09-30 | 2022-01-07 | 成都工具研究所有限公司 | Low-temperature QPQ treatment process for 316L stainless steel workpiece |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR0176720B1 (en) * | 1991-01-30 | 1999-02-18 | 진 폴리 | A method of imparting good corrosion resistance to nitriding and then oxidized ferrous metal products while maintaining the original friction properties |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2679258B1 (en) * | 1991-07-16 | 1993-11-19 | Centre Stephanois Recherc Meca | PROCESS FOR TREATING FERROUS METAL PARTS TO SIMULTANEOUSLY IMPROVE CORROSION RESISTANCE AND FRICTION PROPERTIES THEREOF. |
| FR2708623B1 (en) * | 1993-08-06 | 1995-10-20 | Stephanois Rech Mec | Nitriding process for ferrous metal parts, with improved corrosion resistance. |
| JPH0820877A (en) * | 1994-07-07 | 1996-01-23 | Nippon Parkerizing Co Ltd | Method for producing iron-based metal composite material having excellent corrosion resistance |
-
2011
- 2011-10-13 KR KR1020110104641A patent/KR101290896B1/en active Active
-
2012
- 2012-05-02 WO PCT/KR2012/003438 patent/WO2013054997A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR0176720B1 (en) * | 1991-01-30 | 1999-02-18 | 진 폴리 | A method of imparting good corrosion resistance to nitriding and then oxidized ferrous metal products while maintaining the original friction properties |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200143112A (en) | 2019-06-14 | 2020-12-23 | 현대자동차주식회사 | Ceramic paint composition and brake disc plate for vehicle comprising the same |
| US11649376B2 (en) | 2019-06-14 | 2023-05-16 | Hyundai Motor Company | Ceramic paint composition and brake disc plate for vehicle comprising the same |
| KR102112796B1 (en) * | 2019-12-11 | 2020-05-19 | 신기산업 주식회사 | Method of Mold Part Surface Oxidation Heat Treatment |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2013054997A1 (en) | 2013-04-18 |
| KR20130039947A (en) | 2013-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101290896B1 (en) | Corrosion resistant metal and method for modification of metal surfaces for corrosion resistance improvement using oxynitrocarburising process | |
| EP0217421A2 (en) | Corrosion resistant steel components and method of manufacture thereof | |
| ATE207453T1 (en) | METHOD FOR TREATING WATER CONTAINING HEAVY METALS | |
| CN103502501B (en) | Molten salt bath for nitriding steel mechanical components and method for implementing same | |
| JP2016132784A (en) | Trivalent chromium black chemical conversion coating solution, trivalent chromium-containing water-soluble finishing treatment solution, and metal substrate treatment method | |
| BR9403000A (en) | Nitriding process for parts made of ferrous metal | |
| US3967954A (en) | Pre-leaching or reduction treatment in the beneficiation of titaniferous iron ores | |
| US1930388A (en) | Process for hardening alloy steels | |
| CN110004403A (en) | A kind of compound salt bath ion of rare earth modified multicomponent seeps the modified industry method of processing workpiece | |
| GB138948A (en) | Improvements in or relating to the purification of zinc solutions | |
| KR900007716B1 (en) | Gas Sulfide Nitriding Method | |
| US3632487A (en) | Method of preparing tinplate | |
| TWI589732B (en) | Chemically-treated steel sheet and production method thereof | |
| US3653979A (en) | Process for the production of a steel exhibiting consistently low weight loss test values | |
| JPS60208481A (en) | Production of dead soft cold rolled steel sheet having excellent phosphate treatability | |
| US2903384A (en) | Method of preparing stainless-steel wire for drawing and forming | |
| US976044A (en) | Treatment of precious metalliferous ores. | |
| JP2005240084A (en) | Trivalent chromate plating system | |
| US2771411A (en) | Cyanide compositions suitable for electroplating baths and method for the preparation thereof | |
| CN108866524A (en) | The method of automobile absorber spring preservative treatment | |
| TWI588295B (en) | Chemically-treated steel sheet and production method thereof | |
| GB1020534A (en) | Improvements in the production of a wear-resistant surface on ferrous metal parts | |
| JP2002235193A (en) | Method for forming iron sulfide-based coating with excellent slidability and iron-based material provided with iron sulfide-based coating | |
| DE889292C (en) | Process for the production of a particularly active FeO | |
| US1340480A (en) | Metallurgical process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| PA0109 | Patent application |
Patent event code: PA01091R01D Comment text: Patent Application Patent event date: 20111013 |
|
| PA0201 | Request for examination | ||
| PG1501 | Laying open of application | ||
| E902 | Notification of reason for refusal | ||
| PE0902 | Notice of grounds for rejection |
Comment text: Notification of reason for refusal Patent event date: 20130603 Patent event code: PE09021S01D |
|
| E701 | Decision to grant or registration of patent right | ||
| PE0701 | Decision of registration |
Patent event code: PE07011S01D Comment text: Decision to Grant Registration Patent event date: 20130715 |
|
| GRNT | Written decision to grant | ||
| PR0701 | Registration of establishment |
Comment text: Registration of Establishment Patent event date: 20130723 Patent event code: PR07011E01D |
|
| PR1002 | Payment of registration fee |
Payment date: 20130723 End annual number: 3 Start annual number: 1 |
|
| PG1601 | Publication of registration | ||
| FPAY | Annual fee payment |
Payment date: 20160629 Year of fee payment: 4 |
|
| PR1001 | Payment of annual fee |
Payment date: 20160629 Start annual number: 4 End annual number: 4 |
|
| FPAY | Annual fee payment |
Payment date: 20170626 Year of fee payment: 5 |
|
| PR1001 | Payment of annual fee |
Payment date: 20170626 Start annual number: 5 End annual number: 5 |
|
| FPAY | Annual fee payment |
Payment date: 20180625 Year of fee payment: 6 |
|
| PR1001 | Payment of annual fee |
Payment date: 20180625 Start annual number: 6 End annual number: 6 |
|
| FPAY | Annual fee payment |
Payment date: 20190807 Year of fee payment: 7 |
|
| PR1001 | Payment of annual fee |
Payment date: 20190807 Start annual number: 7 End annual number: 7 |
|
| PR1001 | Payment of annual fee |
Payment date: 20200716 Start annual number: 8 End annual number: 8 |
|
| PR1001 | Payment of annual fee |
Payment date: 20210817 Start annual number: 9 End annual number: 9 |
|
| PR1001 | Payment of annual fee |
Payment date: 20220721 Start annual number: 10 End annual number: 10 |
|
| PR1001 | Payment of annual fee |
Payment date: 20230821 Start annual number: 11 End annual number: 11 |
|
| PR1001 | Payment of annual fee |
Payment date: 20240812 Start annual number: 12 End annual number: 12 |