TW452506B - Corrosion prevention of metals using bis-functional polysulfur silanes - Google Patents
Corrosion prevention of metals using bis-functional polysulfur silanes Download PDFInfo
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- TW452506B TW452506B TW88110554A TW88110554A TW452506B TW 452506 B TW452506 B TW 452506B TW 88110554 A TW88110554 A TW 88110554A TW 88110554 A TW88110554 A TW 88110554A TW 452506 B TW452506 B TW 452506B
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- patent application
- treatment solution
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 69
- 239000002184 metal Substances 0.000 title claims abstract description 69
- 150000004756 silanes Chemical class 0.000 title claims abstract description 7
- 150000002739 metals Chemical class 0.000 title abstract description 8
- 238000005536 corrosion prevention Methods 0.000 title 1
- 238000011282 treatment Methods 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 46
- 238000005260 corrosion Methods 0.000 claims abstract description 42
- 230000007797 corrosion Effects 0.000 claims abstract description 41
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910000077 silane Inorganic materials 0.000 claims abstract description 31
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 230000001588 bifunctional effect Effects 0.000 claims description 23
- 239000010949 copper Substances 0.000 claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 19
- 229910001369 Brass Inorganic materials 0.000 claims description 18
- 239000010951 brass Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 14
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 13
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000011049 filling Methods 0.000 claims description 13
- -1 third group Chemical group 0.000 claims description 10
- 229910000906 Bronze Inorganic materials 0.000 claims description 8
- 239000010974 bronze Substances 0.000 claims description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 8
- 229920001021 polysulfide Polymers 0.000 claims description 8
- 239000005077 polysulfide Substances 0.000 claims description 8
- 150000008117 polysulfides Polymers 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910000838 Al alloy Inorganic materials 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000004575 stone Substances 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 claims description 3
- 229910000851 Alloy steel Inorganic materials 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 239000004576 sand Substances 0.000 claims 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 description 21
- 230000007062 hydrolysis Effects 0.000 description 12
- 238000006460 hydrolysis reaction Methods 0.000 description 12
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- RWLDCNACDPTRMY-UHFFFAOYSA-N 3-triethoxysilyl-n-(3-triethoxysilylpropyl)propan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCNCCC[Si](OCC)(OCC)OCC RWLDCNACDPTRMY-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000001680 brushing effect Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- IBKNSIPMTGYUNZ-UHFFFAOYSA-N ethenyl(methoxy)silane Chemical compound CO[SiH2]C=C IBKNSIPMTGYUNZ-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 235000012054 meals Nutrition 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000007746 phosphate conversion coating Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001709 polysilazane Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- ZRKGYQLXOAHRRN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropylsulfanyl)propyl]silane Chemical class CCO[Si](OCC)(OCC)CCCSCCC[Si](OCC)(OCC)OCC ZRKGYQLXOAHRRN-UHFFFAOYSA-N 0.000 description 2
- XBRBZRDXSFWLCH-UHFFFAOYSA-N 3-(3-diethoxysilylpropyltetrasulfanyl)propyl-diethoxysilane Chemical compound C(C)O[SiH](OCC)CCCSSSSCCC[SiH](OCC)OCC XBRBZRDXSFWLCH-UHFFFAOYSA-N 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910000928 Yellow copper Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000000747 cardiac effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BYOIQYHAYWYSCZ-UHFFFAOYSA-N prop-2-enoxysilane Chemical compound [SiH3]OCC=C BYOIQYHAYWYSCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- IZRJPHXTEXTLHY-UHFFFAOYSA-N triethoxy(2-triethoxysilylethyl)silane Chemical compound CCO[Si](OCC)(OCC)CC[Si](OCC)(OCC)OCC IZRJPHXTEXTLHY-UHFFFAOYSA-N 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical group CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
-
- 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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/53—Treatment of zinc or alloys based thereon
-
- 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
- C23C22/02—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 non-aqueous solutions
-
- 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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/52—Treatment of copper or alloys based thereon
-
- 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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/56—Treatment of aluminium or alloys based thereon
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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
- C23C22/68—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 solutions with pH between 6 and 8
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/16—Sulfur-containing compounds
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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
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Description
4525 06 a? --- B7 五、發明說明（1 ) (請先«讀背面之注$項再填寫本頁) 本發明係有關一種避免金屬表面腐蝕之方法。更特別 而言，本發明提供一種避免金屬表面腐蝕之方法，其包含 提供一種含有一或多種雙功能多硫碎燒之溶液至金屬表面 上。此方法係特別有用於處理鋅、銅'鋁及前述金屬之合 金（諸如，黃銅及青銅）。 大部份之金屬易於改變腐蝕之程度及型式，其將明顯 影響此等金屬及由其製得之產物之性質。雖然許多型式之 腐蝕有時可被避免，但此等步騍係費成本且可能進一步縮 減最終產物之使用性。此外，當聚合物塗覆（諸如，塗料 、黏合劑或橡膠）被施於金屬時，基本金屬材料之腐钮會 造成聚合物塗覆與基本金屬間之黏著性之損失。 經濟部智慧財產局員工消f合作社印製 用以改良金屬（特別是金屬片）之抗腐蝕之習知技術包 含藉由重鉻酸鹽處理使表面成鈍性。但是，此等處理方法 係非所欲的，因為鉻酸鹽離子係具高毒性的且對環境而言 係非所欲者。亦已知者係使用磷酸鹽轉化塗覆物且結合鉻 酸鹽潤濕，以便改良塗料之黏附性及提供腐蝕保護。相信 鉻酸鹽潤濕覆蓋磷酸鹽塗覆物之孔洞，藉此，改良抗腐餘 性及黏附性能。但是’再次地，高度期望能除去一起使用 鉻酸鹽。不幸地’磷酸鹽轉化塗覆物若無鉻酸鹽潤濕一般 係無效的。 最近’各種免除使用鉻酸鹽之技術被提出D其包含以 » 無機矽酸鹽塗覆金屬，其後以有機官能性矽烷處理矽酸鹽 (美國專利第5,108,793號案）。美國專利第5,292,549號案教 示以含有有機官能性矽烷及交聯劑之溶液潤濕金屬 便 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公爱） 經濟部智慧財產局員工費合作ti..1·;':^/. A7 B7 五、發明說明（ 提供暫時之腐姓保護。交聯劑使有機官能性石夕烧交聯而形 ^較密之石夕氧烷膜，是t此專利案之一重大缺點係有機 官能性矽烷不能與金屬表面良好結合，因而美國專利第 ).292,549號案之塗覆物會被輕易洗掉1種用以避免金 屬片腐姓之其它技術亦已被提出。但是，許多此等提出之 技術係無效的’或需耗時，能量不足，多步驟之方法。 避免金屬腐蝕之工作之進—步複雜化係腐蝕可以數種 不同機構產生，其大部份係依其特殊金屬而定。例如，黃 銅對於水性環境之腐蝕（特別是於含有酸性氯化物之溶液 中）及應力腐蝕破裂（特別是氨及胺之存在中）係非常敏感 ϋ銅及銅合金（包含黃鋼）於空氣及含硫之環境中係易於使 去光澤。另一方面，鋅及鋅合金於濕條件下係特別易於形 成白塵”。不幸地’許多用以避免腐蝕之習知技藝之處理 方法對於鋅、辞合金、銅及銅合金係較無效，特別是黃銅 及青銅，或僅對於某些腐蝕有效。 因此’其需求一種簡單之低成本之用以避免金屬表面 (特別是鋅、鋅合金、鋁' 鋁合金 '銅及銅合金（特別是黃 銅及青銅））腐#之技術° 本發明之目的係提供一種避免金屬表面腐蝕之改良方 法 本發明之另一目的係提供用以避免金屬表面腐蝕之處 理溶液。 本發明之另外一目的係提供種避免金屬表面（特別 疋心.鋼.ife及哥.C 屬义公-金·. ΐ腐触之万法
4 5 2 5 0 6 A7 ________ B7 五、發明說明（3 ) 前述目的可依據本發明之一方面藉由提供一種處理金 屬表面以改良抗腐姓性而完成之，其包含之步驟係： (a) 提供金屬表面；及 (b) 提供處理溶液至該金屬表面上，該處理溶液含有 至少一雙官能之多硫矽烷，其係被至少部份水解 ，該矽烷包含：
OR OR
RO-SI—2—Si—OR OR OR 其中（水解前）’每一R係烷基或乙醯基，且2係-Sx或- Q-Sx-Q- ’其中每一q係脂族或芳族基，且义係2至9之整數 (較佳係4)= 每一R可個別選自乙基、曱基、丙基、異丙基、丁基 、異丁基、第二丁基、第三基、及乙酿基。但是需瞭解石夕 烧之水解造成R基（其至少一部份，且較佳係其實質上之全 部）被氩原子取代。每一Q係個別選自Cl_C6烷基（線性或分 枝）、CrC6烯基（線性或分枝）、以一個或多個胺基取代之 Ci-Ce烧基（線性或分枝）、以一個或多個胺基取代之 烯基（線性或分枝）、苯曱基及以C】_c6烷基取代之笨甲基 。一組較佳之矽烷包含具有2至9個硫原子之雙（三乙氧基 矽烷基丙基）硫化物，特別是雙（三乙氧基矽烷基丙基）四 ‘ 硫化物。 本發明之處理方法係特別有用於選自鋅、鋅合金、銅 、銅合金、鋁及鋁合金之金屬。此等金屬表面之例子係黃 本紙張尺度適用中國國家標準（CNS)A4規格（210x297公餐 (請先閱讀背面之注意事項再填寫本頁) -I . I----- — 訂 ------,線 經濟部智慧財產局員工消費合作社印製 A： __________B7_____ 五、發明說明（4 ) 銅、青銅及熱浸漬電錢鋼。 處理溶液較佳係包含水及溶劑，諸如，一或多種之醇 (例如’乙醇、曱醇、丙醇、及異丙醇）。處理溶液中之雙 官能多硫矽烷之總濃度係以體積計為約0.1 %與約25%之間 -更佳係約1 %與約5 d/q之間3較佳實施例包含每一份水為 約3及約20份甲醇（作為溶劑）間。 本發明亦提供一種用以避免金屬基材腐蝕之處理溶液 ’包含至少一雙官能多硫矽烷，其已被至少部份水解，該 矽烷之化學式係：
OR OR
I, I
R〇—Si—Z一Si—OR OR OR 其中（水解前）.每一 R係烷基或乙醯基，且Z係_Sx戍_ Q-Sx-Q…其中每—q係脂族或芳族基，且以系2至9之整數 具有改良抗腐蚀性之金屬表面亦被提供，且包含. (a) 金屬表面；及 (b) 結合至該金屬表面之矽烷塗覆物‘該發燒包人至 少一雙官能多硫矽烷，其已被至少部汾水解咬 雙官能多硫矽烷包含： (請先聞讀背面之;xft>事項再填冩本頁) 裝 蟑------ 經濟部智慧財產局員工消費合..'····"。，.，，
OR OR
I I
R〇—Si—Z—Si—or OR OR
45 25 06 A7 _____B7 五、發明說明（5 ) Q-Sx-Q-，其中每一Q係脂族或芳族基，且乂係2至9之整數 0 美國專利第 3,842，11 卜 3,873489、3,978103及5,405,985 號案皆指示含硫之有機矽烷化合物係可用作為橡膠及金屬 等之反應偶合劑及附著促進劑。因此直覺地本發明之方法 及處理溶液可被用以促進橡膠或其它聚合塗覆物，諸如， 塗料或黏著劑’對金屬基材之黏著性。因此，塗覆表面將 展現改良之抗腐蝕性，而同時對提供於硫矽烷塗覆之金屬 基材之頂部之額外塗覆物提供黏著性促進。 申請人已發現金屬表面（特別是，鋅、鋅合金、鋁、 鋁合金、銅及銅合金之表面）之腐蝕性可藉由施以含有一 或多種雙官能性多硫矽烷之處理溶液而避免，其中該矽烷 已被部份水解。可被用以製備處理溶液之雙官能性多硫矽 烷包含至少一雙官能多硫矽烷，其已被至少部份水解，該 矽烷之化學式係：
OR OR
RO—Si—Z—Si—OR I I
OR OR 其中（水解前），每一 R係院基或乙醯基’且Z係-Sx或- Q-Sx-Q-，其中每一Q係脂族或芳族基，且X係2至9之整蛟 〇 * 含硫矽烷内之每一R可為相同或相異’因此’矽烷可 包含烷氧基及乙醯氧基部份。但是’如下所述，矽烷於處 理溶液中被水解，如此，實質上所有（或至少一部份）R基 本紙張尺度適用中國國家標準（CNS)A4規格（210* 297公釐〉 (讀先閲讀背面之;i意事項再填寫本頁) I :-Λ·_____— —-*-r6j- — I — fit__ 經濟部智慧財產局員工消費合作社印製 經濟邗智慧財產局員工^費合·1::::···:.;··-:“：
AT ___B7____ 五、發明說明（6 ) 被氫原子取代。於較佳實施例中，每一 R可個別選自乙基 、甲基、丙基、異丙基、丁基、異丁基、第二丁基、第三 基、及乙醯基。相似地，雙官能性多硫矽烷内之Q可為相 同或相異。於較佳實施例中，每一 Q係個別選自C^CVJ^ 基（線性或分枝）' 婦基（線性或分枝）、以一個或多個 胺基取代之C】-c &烧基（線性或分枝）' 以一個或多個胺基 取代之C「C6烯基（線性或分枝）、笨甲基及以c「C6烧基取 代之苯甲基。 特別之較佳雙官能性多硫矽烷包含具有2至9個硫原子 之雙（三乙氧基矽烷基丙基）硫化物。此等化合物具有下述 化學式： och2ch3 och2ch3 CH3CH20~Sr C3H6~SX~-C3H6—S*OCH2CH3 OCH2CH3 OCH2CH3 其中x係2至9之整數=一特別之較佳化合物係雙（三乙氧基 名夕烧基丙基.)四硫化物（其稱為雙（三乙氧基夕院基兩基）硫 烧，其中X係4。 申請人已發現上述雙官能基多硫矽烷於辞、鋅合金、 I呂' 紹合金 '銅及銅合金（特別是黃銅及青銅）之表面上提 供不叮預期之較佳腐触保護.·此外，此等含硫5夕按保護多 ‘ 種型式之腐蝕.包含均勻腐蝕'.去鋅化作用及應力腐钱破 請先閱讀背面之;t竟事項再填骂本頁) 裝 . _______，果________ 裂藉由本發明方法提供之腐蝕保護亦優於傳統之鉻酸鹽 為基準之.處理 S避免鉻之沈.積問題.
A7 4525〇6 _____B7__ 五、發明說明（7 ) (請先閱讀背面之注意事項再填寫本頁) 用於本發明之雙官能性多硫矽烷需被水解，如此’矽 烷將結合至金屬表面。水解期間，烷基或乙醞基（即，，,R” 部份）以氫原子取代之。雖然矽烷需被至少部份水解，製 備本發明處理容液之方法一般會造成妙烧之實質上完全水 解。如此處所用者，“部份水解”一辭係指矽烷上之尺基 僅一部份被氩原子取代。較佳者，雙官能性多硫矽烷需被 水解至每一分子上至少二（更佳係實質上所用）之烷基或乙 醯基被以氫原子取代之。 雙官能性多硫石夕院之水解可僅以添加妙烧至醇/水之 混合物而完成之’藉此，形成本發明之處理溶液6 一般， 以醇/水之混合物混合矽烧會造成梦院之水解（實質上所有 R基以氫原子取代）。水實際上水解矽烷，而醇對於確保適 當之矽烷可解性及溶液穩定度係必需。當處理溶液被施用 於金屬表面時’醇亦改良可濕性，且降低乾燥所需時間。 當然’其它適當之溶劑可被使用以替代醇。現今較佳之醇 係曱醇及乙醇，但其它之醇可相似地被使用之（諸如，丙 醇或異丙醇）》可瞭解多於一種醇可被使用之。 經濟部智慧財產局員工消費合作社印製 為製備本發明之處理溶液，醇及水需被先彼此混合， 較佳係以1份水（體積計）約3與約99份醇之間之比例，更佳 係以1份水（體積計）約3與約20份醇之間之比例。完全混合 後’矽烷被添加至醇/水之混合物，完全混合以確保適當 之水解。處理溶液需被混合至少3〇分鐘，且最高達24小時 ’以便確保完全水解（其後所有之尺基以氫原子取代），藉 此形成本發明之處理溶液。 10 本纸張尺度適用中國國家標準（q\】S)A4規格（2]0 X 297公釐） Λ7 -------- B7 '" -------------- 五、發明說明（S ) 本發明之處理溶液之穩定性可藉由於少於室溫（25。(：） 之溫度（更佳係約〇與約2 〇 t：之間）製備及儲存處理溶液而 促進之（例如’硫沈澱抑制）。但是，需注意申請人已證實 良好之避免腐蝕之結合，即使處理溶液於室溫製備及儲存 。此外，處理溶液之曝露於光下需儘可能避免，因為相信 光會降低溶液之穩定性。本發明之處理溶液之pH值一般 不需被改良，只要處理溶液之一般]^(於雙（三乙氧基矽烷 基丙基）四硫化物之情況係約4與約4.5之間）能完全水解， 諸如’藉由添加乙酸或甲醇為之。 基於前述’需瞭解本發明之處理溶液可簡單地包含一 或多種水解（至少部份）之雙官能性多硫矽烷（如上所述）， 較佳係於醇/水之溶液中，之溶液。事實上，本發明處理 溶液之較佳實施例基本上由水解之雙官能性多硫矽烷之溶 液組成。 處理溶液中之雙官能性多硫矽烷之濃度需為以體積計 為約0.1%與約25%之間，更佳係約]與約5%之間。高於此 較佳範圍之濃度非成本有效的，因為未能提供抗腐蝕性之 重大改良且可此導致溶液之不穩定=需注意在此所討論 及界定之矽烷濃度係皆以用以製備處理溶液所用之未水解 雙g能性多碌矽烷之體積（g卩，水解前）與處理溶液之組份 . 之總體積(:即·矽烷 '水及醇）之比例測量此外，此等濃 度洚指用以製備處理溶液之未水解雙官能性多琉矽烷之總 量.因為數矽烷選擇性地可被用於此處理溶液： (锖先閱讀背面之;1意事項再填耳本頁 經濟部智慧时產局0Kx.;s.費合作7.-;:::ϊο 1 li H I - I - tl - n - - -
4525〇6 Α/ -- B? 五、發明說明（9) <請先閱讀背面之汰意事項再填寫本頁) 施以上述處理溶液前需以溶劑及/或鹼清洗（藉由習知技藝 已知技術），以去離子水潤濕，然後使其乾燥。處理溶液 可藉由使金屬浸漬於溶液内（亦稱為，’潤濕”），使溶液喷灑 於金屬表面上或使處理溶液擦或刷於金屬基材上被直接施 於清洗過之金屬（即’金屬與本發明之處理组成物件無其 它層）’浸溃之時間並不重要，因其一般不會影響所形成 之膜厚度或性能。然而’較佳者浸潰時間係約1秒與約30 分鐘之間，更佳係約5秒與約2分鐘之間，以便確保金屬之 完全塗覆。不同於其它之矽烷處理方法，被塗覆之金屬可 於室溫乾燥，因無需加熱或固化矽烷塗覆物。 典型上’乾燥於室溫時會花數分鐘，其部份係依處理 溶液中所提供之水量而定（醇對水之比例減少時，乾燥時 間增加）》雖然數塗覆物可被施用，但一般而言單一塗覆 物係足夠。 上述處理方法已顯示提供不可預期之較優之避免腐蝕 ’特別是對鋅、銅、鋁及前述金屬之合金。如此所用者， 經濟部智慧財產局員Η消費合作社印製 ’’鋼合金”係指其間銅係主要金屬之任何金合（即，無其它 金屬以大於銅之量存在）。鋅合金及銘合金相具相似定義 °本發明之處理方法對於避免黃銅及青銅（典型上包含錫 之銅合金）之腐蝕特別有效β例如，黃銅係高度易被腐蝕 .，特別是於水性環境中之均勻腐蝕，去鋅化作用（特別是 於含酸-氣化物之溶液中）及應力腐蝕破裂（特別是於氨及 胺存在中）。之前，申請人所知之對於黃銅之僅有效避免 腐餘之技術係塗刷，或於形成合金期間（諸如，銅、錫、 12 ®辟標準（CNS)A4規格（210 497公餐） 經濟部智慧財產局具Η消費合.-!1sjd Λ： B7 五、發明說明（10) 鋅所成之黃銅）添加額外金屬至黃銅。但是，塗刷並非绅 是可能或所欲者’諸如’當黃銅被用於藝術雕塑品時，且 添加其它合金元素係昂貴的。但是，申請人發現本發明之 處理方法於避免黃銅腐鞋係非常有效，且無需塗料之外層 。因此’本發明之方法係特別有用且有效於避免黃鋼及青 銅雕塑品之腐姓。 下列範例證實一些藉由使用本發明方法及處理溶液獲 得之較優且不可預期之結果。於所有情況中，金屬基材樣 品先使用標準非钱刻驗清洗液（AC 1 055，可得自Brent America. Inc.)作鹼性清洗。8%之清洗水溶液被加熱至7〇 至80°C ’且金屬基材被浸於熱溶液2_3分鐘。然後基材於 去離子水中潤濕至達成水斷裂自由表面為止。被潤濕之樣 品以壓縮空氣吹乾。 範例1 為比較藉由本發明方法及其它處理技術提供之腐蝕保 護’相同之黃銅樣品（以鹼清洗，冷軋，7〇/3〇黃銅片）以12· 雙_(三乙氧基矽烷基）乙烷(‘‘BTSE，·)、乙烯基曱氧基矽烷 及雙-{二乙氧基矽烷基兩基）胺之溶液及依據本發明之處 理溶液塗覆之。 依據本發明之處理溶液依下述者製備：25毫升之水與 . 4Mi毫升之尹醇完全混合（以體積計每份水為1 8份之甲醇） =其次 25毫并之雙三乙氧基矽烷基丙基）四硫化物被 (讀先閱讀背面之注意事項再填寫本頁> 裝--------.一；----------蟑-------- 镬慢添加至甲醇，水之混合物、而同時混合，藉此.提供
經濟部智慧財產局員工消贄合作社印製 4 5 2 5 06 A7 --------B7 五、發明說明（11) ，以確保矽烷之足夠水解。為避免硫沈澱，溶液被冷凍， 如此’溫度被降至約5 °c。冷凍亦使光排除於處理溶液。 此處理溶液被藉由浸漬施用於冷軋之70/30黃銅片之樣品 。溶液溫度係约5-l〇t，且樣品被浸溃約100秒》塗覆後 ’樣品於室溫之空氣中乾燥。 比較用之1,2-雙·(三乙氧基矽烷基）乙烷（“BTSE，，）、乙 烯基甲氧基矽烷及雙-(三乙氧基矽烷基丙基）胺之處理溶 液以相似方式製備。於所有情況中’矽烷濃度係約5〇/〇， 且醇/水溶劑之混合被使用之。此外’每一溶液pH值被調 整（需要時），以便確保最大水解。BTSE及乙烯基曱氧基 矽烷之pH值係約4至約6，而雙-(三乙氧基矽烷基丙基）胺 之之pH值係約1〇至約π。任何所需之]511值調整可使用乙 酸及氫氧化鈉完成之。鹼清洗之冷軋70/30黃銅片之樣品 以上述相同方式以此等溶液塗覆之。 為模擬海水之腐敍環境，塗覆樣品及未被塗覆之比較 組被部份浸潰於3%NaCl溶液中1000小時。然後移除樣品 且以視覺檢試可看出之腐蝕記號，包含水線攻擊者及任何 褪色。結果被提供於下表中： 樣品 於3%NaCl溶液中1〇〇〇小時後 ' 未塗覆(僅以驗清洗） 嚴重褪色-，鼻銅沈積之水線攻擊存在 BTSE 嚴重褪色，具嚴重銅沈積之水線攻擊^' 乙烯基矽烷 輕微之褪色，水線處之最小銅沈積 ' 雙-(三乙氧基矽烷 基丙基)胺 藍鋼沈積於遨個浸潰區域，嚴重之水線攻擊 雙-(三乙氧基矽烷 基两基)四硫化物 ---------- 與原始外觀無變化 本紙張尺度適用中國國家標準（CNS)A4規格（210 X四7公釐） n I I I n 一。，I I n n I I (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印怎 A7 ----^---- 五·、發明說明（i2) 範例2 黃銅樣品依據上述範例丨所述方法製備之。塗覆之樣 品及未被塗覆之比較組被浸Μ〇2Ν Ηα溶液中5天，以便 檢測本發明處理溶液對次避免去鋅化作用之能力。下述結 果被觀察出： , -----—__ 1 樣品 0.2N HC1溶液中5天後 未被塗覆(僅以鹼清洗） 於整個浸潰區觀察到去辞化 DTCTT ~~~-- b 1 bt 於整個浸潰區觀察到嚴重去鋅化 乙婦基石夕燒 ^整個浸潰區觀察到去辞化 雙-(二乙氧基矽烷基丙 基）四硫化物 與原始外觀無變化（即，無去鋅化） —·~·~- ---.... 範例3 —個頁銅樣品被以鹼清洗，且依據本發明之處理溶液 依據範例1之方法製備。一黃銅樣品未被塗覆，因而作為 比較且未塗覆之樣品被彎曲（1 8〇度）以便提供用以模擬 應力腐蝕破裂之樣品上之高應力@。第二樣品以本發明之 處理心液且依範例1所述方式塗覆，然後本身被彎曲。第 三樣品先本身被變曲'然後以本發明之處理溶液且以範例 1’斤逆方式塗覆，然後所有樣品被曝露於強氨蒸氣18小時 …曝路後，樣品被以視覺檢測腐蝕性，且其後被打開丨 Ρ未被f曲）。下述所提供之結果再次證實本發明處 理’分液對於避免腐蝕之能力.且亦顯示因而提供之塗覆物 係可變形的， --------訂--------- <請先«讀背面之注意事項再填寫本頁) 452506 五、發明說明（⑴ 樣品 曝露於氨蒸氣18小時後 打開彎曲之作用 未塗覆之比較组 整個表面嚴重變黑 樣品於弩曲時斷裂 塗t，然後穹曲 端緣處微小變黑 於彎曲之一端開始彼裂 彎曲，然後塗覆 端緣處微小變黑 無開始破裂 範例4 三個A12024樣品依前述方式以鹼清洗》—樣品作為比 較組，且於鹼清洗後未以任何方式塗覆。第二嵌板接受標 準之鉻酸鹽處理，其係以熟習此項技藝者所知之方式為之 。第三嵌板以此間所述之方式且以範例1所述之雙-(三乙 氧基石夕燒基丙基）四硫化物溶液塗覆。 為檢測塗覆物之可成形性及形成腐蝕性能之任何負面 作用’所有三個樣品於杯狀拉伸機器内被拉伸至約8mm之 深度，以便製備用於Olsen測試之標準杯。因拉伸方法需 要施以潤滑劑至杯之内表面，一些溶液清洗於拉伸後施行 之’以便移除任何油狀之污染物。被拉伸之樣品被完全濕 浸於3%NaCl溶液中一週，然後樣品被視覺觀察腐蝕記號( 内外表面）。 樣品 曝露於2%NaCl溶液ί週後 比較組(僅以鹼清洗） _整個表面變色’拉伸區區更嚴重，樣品上 冬許多點具有白色沈積之痕跡；端緣腐蝕 鉻酸鹽 些微之樣品變色’於拉伸1域更|童；整-個樣品具有白色沈積之痕跡 雙-(三乙氧基矽烷基丙 基)四硫化物 整個樣品為原始外觀，包含拉伸區域；無 痕跡；無端緣腐蝕 ‘” 經濟部智慧財產局員Η消費合作社印製 (請先Μ讀背面之注意事項再填寫本頁) 上述結果證貫用於本發明方法及處理溶液中之含硫矽 烧對於銘及銘合金亦有效。 本紙張尺度適用中國國家標準<CNS)A4規格（210 X 297公g ) 16
M B7 五、發明說明（Μ) 範例5 為檢測本發明方法對於避免鋅及鋅合金（包含，例如 ，熱浸潰電鍵鋼）之作用，標準銳鋅嵌板（主要係鋅，且具 有少於1 %之鈦：可得自Nedzinc)以前述方式以鹼清洗之。 一嵌板未被塗覆，而另一者以範例]之處理溶液塗覆’其 係以其間所述方式為之。三嵌板被接受Buher水平水浸潰 測試（Bultei· Μ卿fact職g c〇mpany 〇f
Missouri所發展出未被塗覆之嵌板於一天後即展現超過 其表面80%之白塵，而依據本發明處理之嵌板於6週之曝 露僅展現5%之白塵= 前述較佳實施例之描述絕非全部涵蓋本發明之可能之 變化’且僅係用以例示及描述之用。明顯之改良及改變對 於熟習此項技藝者基於前述教示而未偏離本發明範圍下係 明顯的。因此，本發明所欲之範圍係界定於申請專利範圍 中= ---------------- π請先闉讀背面Μ浲意事項再填寫本頁> 經濟部智慧財產局員工消費合竹扭印"
Claims (1)
- A8 BS C8 D8 45 25 06 ~、申請專利範圍 '— 1. 一種處理金屬表面以改良抗腐蝕性之方法，其包含之 步驟係： ,^---./-----1 订 (請先《讀背面之注意ί項再填寫本頁) (a) 提供金屬表面；及 (b) 提供處理溶液至該金屬表面上，該處理溶液含有至 少一雙官能之多硫矽烷，其係被至少部份水解，該 矽烷包含： OR OR RO-Si—Z—Si—OR OR OR 其中’每一 R係烷基或乙醯基，且Z係_sx或_q_Sx_q_， 其中每一Q係脂族或芳族基，且\係2至9之整數。 2 ·如申清專利範圍第1項之方法，其中每一 R可個別選自 乙基、甲基、丙基、異丙基、丁基、異丁基、第二丁 基、第三基、及乙醯基。 經濟部中央標準局員工消費合作社印聚 3·如申請專利範圍第2項之方法，其中每一 q係個别選自 C「C6烷基（線性或分枝）、（^-(：6烯基（線性或分枝）、以 一個或多個胺基取代iCrC6烷基（線性或分枝）、以— 個或多個胺基取代之CpC6稀基（線性或分枝）、笨甲基 及以Cj-C6烷基取代之苯甲基。 4.如申請專利範圍第3項之方法，其中該雙官能性多硫石厂 烷包含具有2至9個硫原子之雙-(三乙氧基矽烷基丙基） 疏化物。 5 ·如申請專利範圍第4項之方法，其中該雙官能性多硫石夕 烷包含雙-(三乙氧基矽烷基丙基）四硫化物。 18 本紙浪尺度適用中國國家橾隼（CNS ) Α4規格（2!0Χ297公釐） 哇濟部中央橾隼局員工消費合作，於印絮 A8 B8 CS D8 六、申請專利範圍 6. 如申請專利範圍第1項之方法，其中該金屬係選自：鋅 、鋅合金、銅、銅合金、铭及iS合金。 7. 如申請專利範圍第5項之方法 '其中該金屬係選自鋅、 鋅合金、銅、銅合金、鋁及鋁合金。 8. 如申請專利範圍第1項之方法，其中該金屬包含黃銅或 青铜。 9. 如申請專利範圍第1項之方法，其中X係4。 10. 如申請專利範圍第1項之方法，其中該處理溶液進一步 包含水及溶劑。 11. 如申請專利範圍第1 0項之方法，其中該溶劑包含醇， 且係選自：乙醇、曱醇、丙醇及異丙醇。 12. 如申請專利範圍第1項之方法，其中該處理溶液中之該 雙官能性多硫矽烷之總濃度係以體積計為約0.1 %與約 2 5 %之間。 Π.如申請專利範圍第11項之方法，其中該處理溶液中之 該雙官能性多硫矽烷之總濃度係以體積計為約1 %與約 5%之間= 14.如申請專利範圍第1 3項之方法，其中該醇係甲醇，且 該處理溶液每份水具有約3與約20份之曱醇。 i 5.如申請專利範圍第Η項之方法' 其中該金屬係選自鋅 、鋅合金、銅、銅合金、鋁及鋁合金。 1 6 -種用於避免金屬基材腐蝕之處理溶液 '包含已被至 y部位水解之雙官能性碌矽烷‘該矽烷之化學式係 :;......-—. 訂 (請先閣讀背面之注意事項再填寫本頁) A8 B8 C8 D8 45 25 06 六、申請專利範圍 (j)R OR RO一S i—Z—Si—OR OR OR 其中’每一R係烷基或乙醯基，且Z係-Sx或-Q-Sx-Q-， 其中每一Q係脂族或芳族基，且\係2至9之整數。 17.如申請專利範圍第丨6項之處理溶液，其中每一 R可個 別選自乙基、甲基、丙基、異丙基'丁基、異丁基、 第二丁基、第三基、及乙醯基》 1 8.如申請專利範圍第17項之處理溶液，其中每一 q係個 別選自CrC6烷基（線性或分枝）、Crc6烯基（線性或分 枝）、以一個或多個胺基取代之c】-c6烷基（線性或分枝） 、以一個或多個胺基取代之crc6烯基（線性或分枝）、 笨甲基及以烷基取代之笨甲基。 19.如申請專利範圍第18項之處理溶液，其中該雙官能性 多硫石夕院包含具有2至9個硫原子之雙_(三乙氧基石夕烧 基丙基）琉化物。 20_如申請專利範圍第19項之處理溶液，其中該雙官能性 多硫石夕烧包含雙-(三乙氧基砂烧基丙基）四硫化物。 21·—種具有改良抗腐蝕性之金屬表面，包含： (a) 金屬表面；及 (b) 結合至該金屬表面之石夕貌塗覆物，該石夕院包含至少 一已被至少部份水解之雙官能性多硫矽烷，該雙官 能性多硫矽烷包含： 本紙伕尺度逍用中國國家；^準（CNS) A4現格（210X297公釐） -20 - ----------C— (請先Η讀背面之注$項再填寫本頁) 訂 經濟部中央標率局員工消費合作社印製六 申請專利範圍 鲤濟.郡中央feff局員工消驚合作、社fp.t-i OR OR R〇~Si一Z—Si—OR OR OR 其中·每一R係烷基或乙醯基，且ZS_Sx<_Q-Sx_…， 其中母一 q係脂族或芳族基，且X係2至9之整數。 22. 如申請專利範圍第21項之金屬表面’其中該金屬係選 自鋅、鋅合金 '銅、鋼合金、紹及銘合金s 23. 如申請專利範圍第22項之金屬表面’其中\係4: 2 4 ‘一種處理金屬表面之方法，包含之步驟係： (a)提供金屬表面； 0>)提供至少一雙官能性多硫矽烷，該矽烷包含： OR OR I I RO一Si—2—*Si—OR OR OR 其中’每一R係烷基或乙醯基，且2係_以或·>Sx_Q_ ’其中每一 Q係脂族或芳族基》且\係2至9之整數； (c)至少部份水解該至少一雙官能性多硫矽烷’以便 形成處理溶液；及 (d'丨將a玄處理溶液施於該金屬表面上。 ίΐ] VP A视格· ---------^------ΐτ------.ii (請先聞讀背面之注意事項再填寫本頁)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/104,260 US6162547A (en) | 1998-06-24 | 1998-06-24 | Corrosion prevention of metals using bis-functional polysulfur silanes |
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| TW452506B true TW452506B (en) | 2001-09-01 |
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| US (1) | US6162547A (zh) |
| EP (1) | EP1097259B1 (zh) |
| JP (1) | JP4122135B2 (zh) |
| KR (1) | KR20010071546A (zh) |
| CN (1) | CN1204294C (zh) |
| AT (1) | ATE291108T1 (zh) |
| AU (1) | AU4776799A (zh) |
| BR (1) | BR9911491A (zh) |
| CA (1) | CA2335748C (zh) |
| DE (1) | DE69924256T2 (zh) |
| ES (1) | ES2237118T3 (zh) |
| IL (1) | IL140191A0 (zh) |
| MX (1) | MXPA00012445A (zh) |
| PL (1) | PL345182A1 (zh) |
| TR (1) | TR200003826T2 (zh) |
| TW (1) | TW452506B (zh) |
| WO (1) | WO1999067444A1 (zh) |
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1998
- 1998-06-24 US US09/104,260 patent/US6162547A/en not_active Expired - Lifetime
-
1999
- 1999-06-24 JP JP2000556082A patent/JP4122135B2/ja not_active Expired - Lifetime
- 1999-06-24 AU AU47767/99A patent/AU4776799A/en not_active Abandoned
- 1999-06-24 CA CA 2335748 patent/CA2335748C/en not_active Expired - Lifetime
- 1999-06-24 DE DE1999624256 patent/DE69924256T2/de not_active Expired - Lifetime
- 1999-06-24 ES ES99931159T patent/ES2237118T3/es not_active Expired - Lifetime
- 1999-06-24 KR KR1020007014504A patent/KR20010071546A/ko not_active Application Discontinuation
- 1999-06-24 EP EP19990931159 patent/EP1097259B1/en not_active Expired - Lifetime
- 1999-06-24 TR TR200003826T patent/TR200003826T2/xx unknown
- 1999-06-24 CN CNB998077275A patent/CN1204294C/zh not_active Expired - Fee Related
- 1999-06-24 AT AT99931159T patent/ATE291108T1/de active
- 1999-06-24 IL IL14019199A patent/IL140191A0/xx unknown
- 1999-06-24 WO PCT/EP1999/004371 patent/WO1999067444A1/en active IP Right Grant
- 1999-06-24 BR BR9911491A patent/BR9911491A/pt not_active Application Discontinuation
- 1999-06-24 MX MXPA00012445A patent/MXPA00012445A/es not_active Application Discontinuation
- 1999-06-24 PL PL34518299A patent/PL345182A1/xx unknown
- 1999-08-18 TW TW88110554A patent/TW452506B/zh active
Also Published As
| Publication number | Publication date |
|---|---|
| KR20010071546A (ko) | 2001-07-28 |
| JP2002519505A (ja) | 2002-07-02 |
| CN1204294C (zh) | 2005-06-01 |
| AU4776799A (en) | 2000-01-10 |
| CA2335748A1 (en) | 1999-12-29 |
| MXPA00012445A (es) | 2002-04-24 |
| CA2335748C (en) | 2008-01-08 |
| ATE291108T1 (de) | 2005-04-15 |
| WO1999067444A1 (en) | 1999-12-29 |
| DE69924256T2 (de) | 2005-08-04 |
| PL345182A1 (en) | 2001-12-03 |
| ES2237118T3 (es) | 2005-07-16 |
| CN1306586A (zh) | 2001-08-01 |
| IL140191A0 (en) | 2002-02-10 |
| EP1097259A1 (en) | 2001-05-09 |
| BR9911491A (pt) | 2001-03-20 |
| EP1097259B1 (en) | 2005-03-16 |
| TR200003826T2 (tr) | 2001-06-21 |
| JP4122135B2 (ja) | 2008-07-23 |
| US6162547A (en) | 2000-12-19 |
| DE69924256D1 (de) | 2005-04-21 |
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