US20190316261A1 - Sealing Composition - Google Patents
Sealing Composition Download PDFInfo
- Publication number
- US20190316261A1 US20190316261A1 US16/325,010 US201716325010A US2019316261A1 US 20190316261 A1 US20190316261 A1 US 20190316261A1 US 201716325010 A US201716325010 A US 201716325010A US 2019316261 A1 US2019316261 A1 US 2019316261A1
- Authority
- US
- United States
- Prior art keywords
- composition
- substrate
- ppm
- conversion
- group
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 494
- 238000007789 sealing Methods 0.000 title claims abstract description 186
- 239000000758 substrate Substances 0.000 claims abstract description 269
- 238000006243 chemical reaction Methods 0.000 claims abstract description 236
- 229910052751 metal Inorganic materials 0.000 claims abstract description 219
- 239000002184 metal Substances 0.000 claims abstract description 219
- 150000001768 cations Chemical class 0.000 claims abstract description 114
- 238000000034 method Methods 0.000 claims abstract description 74
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 53
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 53
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229940006487 lithium cation Drugs 0.000 claims abstract description 29
- 150000002739 metals Chemical class 0.000 claims abstract description 24
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 21
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003556 assay Methods 0.000 claims abstract description 13
- 238000004876 x-ray fluorescence Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 130
- 150000001875 compounds Chemical class 0.000 claims description 87
- 150000003839 salts Chemical class 0.000 claims description 71
- 238000005260 corrosion Methods 0.000 claims description 56
- 230000007797 corrosion Effects 0.000 claims description 56
- 239000007921 spray Substances 0.000 claims description 38
- 229910052782 aluminium Inorganic materials 0.000 claims description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 32
- 230000007935 neutral effect Effects 0.000 claims description 28
- 238000004140 cleaning Methods 0.000 claims description 25
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 21
- 229910052744 lithium Inorganic materials 0.000 claims description 21
- 230000009467 reduction Effects 0.000 claims description 17
- 229910000838 Al alloy Inorganic materials 0.000 claims description 13
- 229910052684 Cerium Inorganic materials 0.000 claims description 13
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 13
- 238000011282 treatment Methods 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052727 yttrium Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 115
- 238000013019 agitation Methods 0.000 description 99
- 239000008367 deionised water Substances 0.000 description 97
- 229910021641 deionized water Inorganic materials 0.000 description 85
- 239000008199 coating composition Substances 0.000 description 84
- 239000010410 layer Substances 0.000 description 83
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 75
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 66
- 238000000576 coating method Methods 0.000 description 63
- 238000007739 conversion coating Methods 0.000 description 63
- -1 VIB cations Chemical class 0.000 description 59
- 239000011248 coating agent Substances 0.000 description 41
- 239000000463 material Substances 0.000 description 37
- 238000007654 immersion Methods 0.000 description 35
- 229920000642 polymer Polymers 0.000 description 35
- 238000012360 testing method Methods 0.000 description 33
- 229910021645 metal ion Inorganic materials 0.000 description 27
- 239000000126 substance Substances 0.000 description 26
- 239000002904 solvent Substances 0.000 description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 24
- 229910019142 PO4 Inorganic materials 0.000 description 23
- 235000021317 phosphate Nutrition 0.000 description 23
- 239000010452 phosphate Substances 0.000 description 22
- 229920005989 resin Polymers 0.000 description 22
- 239000011347 resin Substances 0.000 description 22
- 239000004744 fabric Substances 0.000 description 19
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 18
- 238000001723 curing Methods 0.000 description 18
- 239000008399 tap water Substances 0.000 description 18
- 235000020679 tap water Nutrition 0.000 description 18
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 17
- 125000000129 anionic group Chemical group 0.000 description 17
- 229910052804 chromium Inorganic materials 0.000 description 17
- 239000011651 chromium Substances 0.000 description 17
- 229910003002 lithium salt Inorganic materials 0.000 description 17
- 159000000002 lithium salts Chemical class 0.000 description 17
- 125000002091 cationic group Chemical group 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 16
- 229920001451 polypropylene glycol Polymers 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000004615 ingredient Substances 0.000 description 14
- 230000000737 periodic effect Effects 0.000 description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 239000002253 acid Substances 0.000 description 13
- 239000007800 oxidant agent Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 238000005507 spraying Methods 0.000 description 13
- 230000002378 acidificating effect Effects 0.000 description 12
- 150000001450 anions Chemical class 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 12
- 229910052808 lithium carbonate Inorganic materials 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 238000007598 dipping method Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- 239000012736 aqueous medium Substances 0.000 description 9
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 9
- 238000000151 deposition Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 229910052725 zinc Inorganic materials 0.000 description 9
- RRRCKIRSVQAAAS-UHFFFAOYSA-N 4-[3-(3,4-dihydroxyphenyl)-1,1-dioxo-2,1$l^{6}-benzoxathiol-3-yl]benzene-1,2-diol Chemical compound C1=C(O)C(O)=CC=C1C1(C=2C=C(O)C(O)=CC=2)C2=CC=CC=C2S(=O)(=O)O1 RRRCKIRSVQAAAS-UHFFFAOYSA-N 0.000 description 8
- POJWUDADGALRAB-UHFFFAOYSA-N allantoin Chemical compound NC(=O)NC1NC(=O)NC1=O POJWUDADGALRAB-UHFFFAOYSA-N 0.000 description 8
- 229910052750 molybdenum Inorganic materials 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- ORZHVTYKPFFVMG-UHFFFAOYSA-N xylenol orange Chemical compound OC(=O)CN(CC(O)=O)CC1=C(O)C(C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C=C(CN(CC(O)=O)CC(O)=O)C(O)=C(C)C=2)=C1 ORZHVTYKPFFVMG-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 7
- 238000004070 electrodeposition Methods 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 6
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 229910052720 vanadium Inorganic materials 0.000 description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 6
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000001680 brushing effect Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical class C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- 239000000080 wetting agent Substances 0.000 description 4
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 4
- 229910000165 zinc phosphate Inorganic materials 0.000 description 4
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 3
- GDGIVSREGUOIJZ-UHFFFAOYSA-N 5-amino-3h-1,3,4-thiadiazole-2-thione Chemical compound NC1=NN=C(S)S1 GDGIVSREGUOIJZ-UHFFFAOYSA-N 0.000 description 3
- POJWUDADGALRAB-PVQJCKRUSA-N Allantoin Natural products NC(=O)N[C@@H]1NC(=O)NC1=O POJWUDADGALRAB-PVQJCKRUSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 239000005749 Copper compound Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 229910001297 Zn alloy Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229920000180 alkyd Polymers 0.000 description 3
- 229960000458 allantoin Drugs 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- 150000001880 copper compounds Chemical class 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003269 fluorescent indicator Substances 0.000 description 3
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- GBHRVZIGDIUCJB-UHFFFAOYSA-N hydrogenphosphite Chemical class OP([O-])[O-] GBHRVZIGDIUCJB-UHFFFAOYSA-N 0.000 description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 150000002751 molybdenum Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 229910052706 scandium Inorganic materials 0.000 description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 3
- 229910000693 sodium vanadium oxide Inorganic materials 0.000 description 3
- GPTONYMQFTZPKC-UHFFFAOYSA-N sulfamethoxydiazine Chemical compound N1=CC(OC)=CN=C1NS(=O)(=O)C1=CC=C(N)C=C1 GPTONYMQFTZPKC-UHFFFAOYSA-N 0.000 description 3
- 229910001456 vanadium ion Inorganic materials 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- QUKGLNCXGVWCJX-UHFFFAOYSA-N 1,3,4-thiadiazol-2-amine Chemical compound NC1=NN=CS1 QUKGLNCXGVWCJX-UHFFFAOYSA-N 0.000 description 2
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 2
- HGPSVOAVAYJEIJ-XDHOZWIPSA-N 2-[(e)-(3,4-dihydroxyphenyl)-(3-hydroxy-4-oxoniumylidenecyclohexa-2,5-dien-1-ylidene)methyl]benzenesulfonate Chemical compound C1=CC(=O)C(O)=C\C1=C(C=1C(=CC=CC=1)S(O)(=O)=O)/C1=CC=C(O)C(O)=C1 HGPSVOAVAYJEIJ-XDHOZWIPSA-N 0.000 description 2
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 2
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- WZUVPPKBWHMQCE-UHFFFAOYSA-N Haematoxylin Chemical compound C12=CC(O)=C(O)C=C2CC2(O)C1C1=CC=C(O)C(O)=C1OC2 WZUVPPKBWHMQCE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Chemical class [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013626 chemical specie Substances 0.000 description 2
- 229940117975 chromium trioxide Drugs 0.000 description 2
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- YEOCHZFPBYUXMC-UHFFFAOYSA-L copper benzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 YEOCHZFPBYUXMC-UHFFFAOYSA-L 0.000 description 2
- 150000004699 copper complex Chemical class 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical class [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- YPJRHEKCFKOVRT-UHFFFAOYSA-N lerociclib Chemical compound C1CN(C(C)C)CCN1C(C=N1)=CC=C1NC1=NC=C(C=C2N3C4(CCCCC4)CNC2=O)C3=N1 YPJRHEKCFKOVRT-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 125000005341 metaphosphate group Chemical group 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052605 nesosilicate Inorganic materials 0.000 description 2
- 150000004762 orthosilicates Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- JLGUDDVSJCOLTN-UHFFFAOYSA-N strontium;oxido-(oxido(dioxo)chromio)oxy-dioxochromium Chemical compound [Sr+2].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JLGUDDVSJCOLTN-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-UHFFFAOYSA-J 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- ASTWEMOBIXQPPV-UHFFFAOYSA-K trisodium;phosphate;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[O-]P([O-])([O-])=O ASTWEMOBIXQPPV-UHFFFAOYSA-K 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- 150000003681 vanadium Chemical class 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- SHVRRGGZMBWAJT-ODZAUARKSA-N (z)-but-2-enedioic acid;copper Chemical compound [Cu].OC(=O)\C=C/C(O)=O SHVRRGGZMBWAJT-ODZAUARKSA-N 0.000 description 1
- NCYNKWQXFADUOZ-UHFFFAOYSA-N 1,1-dioxo-2,1$l^{6}-benzoxathiol-3-one Chemical compound C1=CC=C2C(=O)OS(=O)(=O)C2=C1 NCYNKWQXFADUOZ-UHFFFAOYSA-N 0.000 description 1
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 1
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical class C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- VVXLFFIFNVKFBD-UHFFFAOYSA-N 4,4,4-trifluoro-1-phenylbutane-1,3-dione Chemical compound FC(F)(F)C(=O)CC(=O)C1=CC=CC=C1 VVXLFFIFNVKFBD-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 1
- REPMZEQSQQAHJR-UHFFFAOYSA-N 7-(diethylamino)-3,4-dioxo-10H-phenoxazine-1-carboxamide hydrochloride Chemical compound [Cl-].OC(=[NH2+])C1=CC(=O)C(=O)C2=C1NC1=CC=C(N(CC)CC)C=C1O2 REPMZEQSQQAHJR-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XDAWKGNNSZSONL-UHFFFAOYSA-J C(C(O)C)(=O)[O-].[Mo+4].C(C(O)C)(=O)[O-].C(C(O)C)(=O)[O-].C(C(O)C)(=O)[O-] Chemical compound C(C(O)C)(=O)[O-].[Mo+4].C(C(O)C)(=O)[O-].C(C(O)C)(=O)[O-].C(C(O)C)(=O)[O-] XDAWKGNNSZSONL-UHFFFAOYSA-J 0.000 description 1
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical compound [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- OVBJJZOQPCKUOR-UHFFFAOYSA-L EDTA disodium salt dihydrate Chemical compound O.O.[Na+].[Na+].[O-]C(=O)C[NH+](CC([O-])=O)CC[NH+](CC([O-])=O)CC([O-])=O OVBJJZOQPCKUOR-UHFFFAOYSA-L 0.000 description 1
- 229940120146 EDTMP Drugs 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 229910003638 H2SiF6 Inorganic materials 0.000 description 1
- 229910004039 HBF4 Inorganic materials 0.000 description 1
- 101100458658 Homo sapiens MUC13 gene Proteins 0.000 description 1
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 102100023124 Mucin-13 Human genes 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- HGPSVOAVAYJEIJ-UNOMPAQXSA-N O=C1C=C/C(=C(\C2=CC=C(O)C(O)=C2)C2=C(S(=O)(=O)O)C=CC=C2)C=C1O Chemical compound O=C1C=C/C(=C(\C2=CC=C(O)C(O)=C2)C2=C(S(=O)(=O)O)C=CC=C2)C=C1O HGPSVOAVAYJEIJ-UNOMPAQXSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 229910009253 Y(NO3)3 Inorganic materials 0.000 description 1
- CIOMGYGRGMIGFM-UHFFFAOYSA-I [F-].[F-].[F-].[F-].[F-].[Al+3].[Zn++] Chemical compound [F-].[F-].[F-].[F-].[F-].[Al+3].[Zn++] CIOMGYGRGMIGFM-UHFFFAOYSA-I 0.000 description 1
- AYMPTTNSIGVDLT-UHFFFAOYSA-N [O-][N+]([O-])=O.Cl.Cl Chemical compound [O-][N+]([O-])=O.Cl.Cl AYMPTTNSIGVDLT-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001251 acridines Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012556 adjustment buffer Substances 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- AWUCVROLDVIAJX-UHFFFAOYSA-N alpha-glycerophosphate Natural products OCC(O)COP(O)(O)=O AWUCVROLDVIAJX-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical class [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 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 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- RYXHOMYVWAEKHL-UHFFFAOYSA-N astatine atom Chemical compound [At] RYXHOMYVWAEKHL-UHFFFAOYSA-N 0.000 description 1
- PLBXHDJCRPSEEY-UHFFFAOYSA-N azane;2-hydroxyacetic acid;zirconium Chemical compound N.[Zr].OCC(O)=O PLBXHDJCRPSEEY-UHFFFAOYSA-N 0.000 description 1
- VEGSIXIYQSUOQG-UHFFFAOYSA-N azane;2-hydroxypropanoic acid;zirconium Chemical compound [NH4+].[Zr].CC(O)C([O-])=O VEGSIXIYQSUOQG-UHFFFAOYSA-N 0.000 description 1
- RJMWSMMKKAJPGD-UHFFFAOYSA-L azanium;2-hydroxypropane-1,2,3-tricarboxylate;zirconium(2+) Chemical compound [NH4+].[Zr+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O RJMWSMMKKAJPGD-UHFFFAOYSA-L 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- UDSAIICHUKSCKT-UHFFFAOYSA-N bromophenol blue Chemical compound C1=C(Br)C(O)=C(Br)C=C1C1(C=2C=C(Br)C(O)=C(Br)C=2)C2=CC=CC=C2S(=O)(=O)O1 UDSAIICHUKSCKT-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- MGIWDIMSTXWOCO-UHFFFAOYSA-N butanedioic acid;copper Chemical compound [Cu].OC(=O)CCC(O)=O MGIWDIMSTXWOCO-UHFFFAOYSA-N 0.000 description 1
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 1
- VBRNLOQCBCPPHL-UHFFFAOYSA-N calmagite Chemical compound CC1=CC=C(O)C(N=NC=2C3=CC=CC=C3C(=CC=2O)S(O)(=O)=O)=C1 VBRNLOQCBCPPHL-UHFFFAOYSA-N 0.000 description 1
- 235000015116 cappuccino Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- JAJGBCGKZWPSDR-UHFFFAOYSA-N cerium(3+) nitric acid trinitrate Chemical compound [N+](=O)(O)[O-].[N+](=O)([O-])[O-].[Ce+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] JAJGBCGKZWPSDR-UHFFFAOYSA-N 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- SXYCCJAPZKHOLS-UHFFFAOYSA-N chembl2008674 Chemical compound [O-][N+](=O)C1=CC=C2C(N=NC3=C4C=CC=CC4=CC=C3O)=C(O)C=C(S(O)(=O)=O)C2=C1 SXYCCJAPZKHOLS-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229940108925 copper gluconate Drugs 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- IEDRGHHDYMVJLD-UHFFFAOYSA-N copper potassium tricyanide Chemical compound [K+].[Cu++].[C-]#N.[C-]#N.[C-]#N IEDRGHHDYMVJLD-UHFFFAOYSA-N 0.000 description 1
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- LHBCBDOIAVIYJI-DKWTVANSSA-L copper;(2s)-2-aminobutanedioate Chemical compound [Cu+2].[O-]C(=O)[C@@H](N)CC([O-])=O LHBCBDOIAVIYJI-DKWTVANSSA-L 0.000 description 1
- HIAAPJWEVOPQRI-DFWYDOINSA-L copper;(2s)-2-aminopentanedioate Chemical compound [Cu+2].[O-]C(=O)[C@@H](N)CCC([O-])=O HIAAPJWEVOPQRI-DFWYDOINSA-L 0.000 description 1
- FXGNPUJCPZJYKO-TYYBGVCCSA-L copper;(e)-but-2-enedioate Chemical compound [Cu+2].[O-]C(=O)\C=C\C([O-])=O FXGNPUJCPZJYKO-TYYBGVCCSA-L 0.000 description 1
- RSJOBNMOMQFPKQ-UHFFFAOYSA-L copper;2,3-dihydroxybutanedioate Chemical compound [Cu+2].[O-]C(=O)C(O)C(O)C([O-])=O RSJOBNMOMQFPKQ-UHFFFAOYSA-L 0.000 description 1
- CMRVDFLZXRTMTH-UHFFFAOYSA-L copper;2-carboxyphenolate Chemical compound [Cu+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O CMRVDFLZXRTMTH-UHFFFAOYSA-L 0.000 description 1
- WMYBXRITVYIFCO-UHFFFAOYSA-N copper;2-hydroxybutanedioic acid Chemical compound [Cu].OC(=O)C(O)CC(O)=O WMYBXRITVYIFCO-UHFFFAOYSA-N 0.000 description 1
- DYROSKSLMAPFBZ-UHFFFAOYSA-L copper;2-hydroxypropanoate Chemical compound [Cu+2].CC(O)C([O-])=O.CC(O)C([O-])=O DYROSKSLMAPFBZ-UHFFFAOYSA-L 0.000 description 1
- PUHAKHQMSBQAKT-UHFFFAOYSA-L copper;butanoate Chemical compound [Cu+2].CCCC([O-])=O.CCCC([O-])=O PUHAKHQMSBQAKT-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- LLVVIWYEOKVOFV-UHFFFAOYSA-L copper;diiodate Chemical compound [Cu+2].[O-]I(=O)=O.[O-]I(=O)=O LLVVIWYEOKVOFV-UHFFFAOYSA-L 0.000 description 1
- CHPMNDHAIUIBSK-UHFFFAOYSA-J copper;disodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;tetrahydrate Chemical compound O.O.O.O.[Na+].[Na+].[Cu+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O CHPMNDHAIUIBSK-UHFFFAOYSA-J 0.000 description 1
- BQVVSSAWECGTRN-UHFFFAOYSA-L copper;dithiocyanate Chemical compound [Cu+2].[S-]C#N.[S-]C#N BQVVSSAWECGTRN-UHFFFAOYSA-L 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- PJBGIAVUDLSOKX-UHFFFAOYSA-N copper;propanedioic acid Chemical compound [Cu].OC(=O)CC(O)=O PJBGIAVUDLSOKX-UHFFFAOYSA-N 0.000 description 1
- LZJJVTQGPPWQFS-UHFFFAOYSA-L copper;propanoate Chemical compound [Cu+2].CCC([O-])=O.CCC([O-])=O LZJJVTQGPPWQFS-UHFFFAOYSA-L 0.000 description 1
- HWDGVJUIHRPKFR-UHFFFAOYSA-I copper;trisodium;18-(2-carboxylatoethyl)-20-(carboxylatomethyl)-12-ethenyl-7-ethyl-3,8,13,17-tetramethyl-17,18-dihydroporphyrin-21,23-diide-2-carboxylate Chemical compound [Na+].[Na+].[Na+].[Cu+2].N1=C(C(CC([O-])=O)=C2C(C(C)C(C=C3C(=C(C=C)C(=C4)[N-]3)C)=N2)CCC([O-])=O)C(=C([O-])[O-])C(C)=C1C=C1C(CC)=C(C)C4=N1 HWDGVJUIHRPKFR-UHFFFAOYSA-I 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- RXCBCUJUGULOGC-UHFFFAOYSA-H dipotassium;tetrafluorotitanium;difluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Ti+4] RXCBCUJUGULOGC-UHFFFAOYSA-H 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000008377 fluorones Chemical class 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- ADAUKUOAOMLVSN-UHFFFAOYSA-N gallocyanin Chemical compound [Cl-].OC(=O)C1=CC(O)=C(O)C2=[O+]C3=CC(N(C)C)=CC=C3N=C21 ADAUKUOAOMLVSN-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- TZNXTUDMYCRCAP-UHFFFAOYSA-N hafnium(4+);tetranitrate Chemical compound [Hf+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O TZNXTUDMYCRCAP-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- BSZKBMAGLBURDO-UHFFFAOYSA-J hydrogen carbonate;zirconium(4+) Chemical class [Zr+4].OC([O-])=O.OC([O-])=O.OC([O-])=O.OC([O-])=O BSZKBMAGLBURDO-UHFFFAOYSA-J 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000003854 isothiazoles Chemical class 0.000 description 1
- 150000002545 isoxazoles Chemical class 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 150000002601 lanthanoid compounds Chemical class 0.000 description 1
- 229940071145 lauroyl sarcosinate Drugs 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- PSACBMCCZLGPIA-UHFFFAOYSA-J molybdenum(4+) tetraformate Chemical compound C(=O)[O-].[Mo+4].C(=O)[O-].C(=O)[O-].C(=O)[O-] PSACBMCCZLGPIA-UHFFFAOYSA-J 0.000 description 1
- JVPZBIONBZVCED-UHFFFAOYSA-J molybdenum(4+) tetrasulfamate Chemical compound S(N)([O-])(=O)=O.[Mo+4].S(N)([O-])(=O)=O.S(N)([O-])(=O)=O.S(N)([O-])(=O)=O JVPZBIONBZVCED-UHFFFAOYSA-J 0.000 description 1
- TXCOQXKFOPSCPZ-UHFFFAOYSA-J molybdenum(4+);tetraacetate Chemical compound [Mo+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O TXCOQXKFOPSCPZ-UHFFFAOYSA-J 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- YOYLLRBMGQRFTN-SMCOLXIQSA-N norbuprenorphine Chemical compound C([C@@H](NCC1)[C@]23CC[C@]4([C@H](C3)C(C)(O)C(C)(C)C)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YOYLLRBMGQRFTN-SMCOLXIQSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- DAWBXZHBYOYVLB-UHFFFAOYSA-J oxalate;zirconium(4+) Chemical compound [Zr+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O DAWBXZHBYOYVLB-UHFFFAOYSA-J 0.000 description 1
- 150000004893 oxazines Chemical class 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000003853 pentazoles Chemical class 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 150000005053 phenanthridines Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- ZDHURYWHEBEGHO-UHFFFAOYSA-N potassiopotassium Chemical compound [K].[K] ZDHURYWHEBEGHO-UHFFFAOYSA-N 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- AWUCVROLDVIAJX-GSVOUGTGSA-N sn-glycerol 3-phosphate Chemical compound OC[C@@H](O)COP(O)(O)=O AWUCVROLDVIAJX-GSVOUGTGSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940079841 sodium copper chlorophyllin Drugs 0.000 description 1
- 235000013758 sodium copper chlorophyllin Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- UPDATVKGFTVGQJ-UHFFFAOYSA-N sodium;azane Chemical compound N.[Na+] UPDATVKGFTVGQJ-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 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
- 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
-
- 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
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
- C23C22/66—Treatment of aluminium 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
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/372—Phosphates of heavy metals of titanium, vanadium, zirconium, niobium, hafnium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/12—Wash primers
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
-
- 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
- C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
- C23C22/26—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds containing also organic compounds
- C23C22/27—Acids
-
- 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
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/361—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
-
- 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
- C23C22/50—Treatment of iron 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
- C23C22/53—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
- C23C22/05—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
- C23C22/54—Treatment of refractory metals 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
- C23C22/57—Treatment of magnesium 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
- C23C22/58—Treatment of other metallic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
-
- 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
- C23C22/78—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
- 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
- C23C22/82—After-treatment
-
- 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
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/16—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions using inhibitors
- C23G1/18—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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/22—Light metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/20—Pretreatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
Definitions
- the present invention relates to sealing compositions and methods for treating a metal substrate.
- the present invention also relates to a coated metal substrate.
- an inorganic protective coating can be applied to the metal surface.
- This inorganic protective coating also referred to as a conversion coating, may be the only coating applied to the metal, or the coating can be an intermediate coating to which subsequent coatings are applied.
- Chromate based coatings are currently used as inorganic conversion coatings because they provide corrosion resistant properties and adhesion for application of subsequent coatings.
- environmentally safer conversion coatings that can provide corrosion resistance to an underlying metal surface and adhesion to subsequently applied coatings.
- Cerium and other rare earth element containing coatings have been identified as potential replacements for chromate based coatings in metal finishing. These coatings include cerium and other rare earth element containing coatings that are formed by various processes such as immersion, electroplating from a cerium nitrate solution, plating from an acidic cerium chloride containing solution and an oxidant (at elevated temperatures), as well as multi-step processes, and electrolytic and non-electrolytic processes having a sealing step.
- At least some of the coatings prepared using these compositions and methods do not perform as well as those formed using chromate treatments and/or can develop corrosion and/or pits on the surface.
- at least some of the cerium and other rare earth element-containing coatings known in the art can also suffer from one or more of the following disadvantages: (1) a tendency of the rare earth element to precipitate in solution away from the metal surface in the form of a sludge-like material; (2) difficulty in obtaining a uniform coating which does not tend to over-coat and exhibit poor adhesion to the substrate; (3) the necessity to use multiple steps and extensive periods of time to deposit a coating; and (4) the necessity to use specific conversions and solution compositions in order to coat multiply alloys, especially aluminum 2024 alloys.
- a method of treating a substrate comprising: contacting at least a portion of the substrate surface with a sealing composition comprising a lithium cation.
- the method may further comprise contacting at least a portion of the substrate with a lanthanide series metal cation, a Group IIIB metal cation, a Group IVB metal cation, or a combination thereof.
- the sealing composition may be applied to provide a layer of the dried sealing composition having a thickness of 5 nm to 550 nm.
- a system for treating a substrate comprising: a conversion composition for treating at a least a portion of the substrate, the conversion composition comprising a lanthanide series metal cation, a Group IIIB metal cation, a Group IVB metal cation, or a combination thereof; and a sealing composition for treating at least a portion of the substrate, the sealing composition comprising a lithium cation.
- substrates obtainable by the system and/or methods.
- FIG. 1 shows a schematic illustrating thickness of a layer of the sealing composition on a substrate surface.
- a system for treating a substrate comprising, or in some instances, consisting essentially of, or in some instances, consisting of, a sealing composition comprising, or in instances, consisting essentially of, or in some instances, consisting of, a lithium cation.
- the system may further comprise, or in some instances consist essentially of, or in some instances, consist of, a conversion composition comprising, or in some instances, consisting essentially of, or in some instances, consisting of, a lanthanide series metal cation, a Group IIIB metal cation, a Group IVB metal cation, or a combination thereof.
- the system may further comprise, or consist essentially of, or consist of, a cleaning composition and/or a deoxidizer.
- a method of treating a substrate comprising, or in some instances, consisting essentially of, or in some instances, consisting of: contacting at least a portion of the substrate surface with a sealing composition comprising, or in some instances, consisting essentially of, or in some instances, consisting of, a lithium cation.
- the method may also comprise, or in some instances, consist essentially of, or in some instances, consist of, contacting at least a portion of the substrate surface with a conversion composition comprising, or in some instances, consisting essentially of, or in some instances, consisting of, a lanthanide series metal cation, a Group IIIB metal cation, a Group IVB metal cation, or a combination thereof.
- a substrate treated with the system and/or method of the present invention may comprise, or in some instances consist essentially of, or in some instances, consist of, a layer formed from the sealing composition comprising a lithium cation.
- the substrate may further comprise a film or a layer formed from the conversion composition comprising cations of a lanthanide series metal, a Group IIIB metal, and/or a Group IVB metal.
- Suitable substrates that may be used in the present invention include metal substrates, metal alloy substrates, and/or substrates that have been metallized, such as nickel plated plastic.
- the metal or metal alloy can comprise or be steel, aluminum, zinc, nickel, and/or magnesium.
- the steel substrate could be cold rolled steel, hot rolled steel, electrogalvanized steel, and/or hot dipped galvanized steel.
- Aluminum alloys of the 1XXX, 2XXX, 3XXX, 4XXX, 5XXX, 6XXX, or 7XXX series as well as clad aluminum alloys also may be used as the substrate.
- Aluminum alloys may comprise 0.01% by weight copper to 10% by weight copper.
- Aluminum alloys which are treated may also include castings, such as 1XX.X, 2XX.X, 3XX.X, 4XX.X, 5XX.X, 6XX.X, 7XX.X, 8XX.X, or 9XX.X (e.g.: A356.0).
- Magnesium alloys of the AZ31B, AZ91C, AM60B, or EV31A series also may be used as the substrate.
- the substrate used in the present invention may also comprise titanium and/or titanium alloys, zinc and/or zinc alloys, and/or nickel and/or nickel alloys.
- the substrate may comprise a portion of a vehicle such as a vehicular body (e.g., without limitation, door, body panel, trunk deck lid, roof panel, hood, roof and/or stringers, rivets, landing gear components, and/or skins used on an aircraft) and/or a vehicular frame.
- a vehicular body e.g., without limitation, door, body panel, trunk deck lid, roof panel, hood, roof and/or stringers, rivets, landing gear components, and/or skins used on an aircraft
- vehicular body e.g., without limitation, door, body panel, trunk deck lid, roof panel, hood, roof and/or stringers, rivets, landing gear components, and/or skins used on an aircraft
- vehicle or variations thereof includes, but is not limited to, civilian, commercial and military aircraft, and/or land vehicles such as cars, motorcycles, and/or trucks.
- the sealing composition may comprise a lithium cation.
- the lithium cation may be in the form of a lithium salt.
- the sealing composition also may further comprise at least one Group IA metal cation other than lithium, a Group VB metal cation, and/or Group VIB metal cation.
- the at least one Group IA metal cation other than lithium, a Group VB metal cation, and/or Group VIB metal cation may be in the form of a salt.
- Nonlimiting examples of anions suitable for forming a salt with the lithium, Group IA cations other than lithium, Group VB cations, and/or Group VIB cations include carbonates, hydroxides, nitrates, halogens, sulfates, phosphates and silicates (e.g., orthosilicates and metasilicates) such that the metal salt may comprise a carbonate, an hydroxide, a nitrate, a halide, a sulfate, a phosphate, a silicate (e.g., orthosilicate or metasilicate), a permanganate, a chromate, a vanadate, a molybdate, and/or a perchlorate.
- anions suitable for forming a salt with the lithium, Group IA cations other than lithium, Group VB cations, and/or Group VIB cations include carbonates, hydroxides, nitrates, halogens,
- the metal salts of the sealing composition each may be present in the sealing composition in an amount of at least 25 ppm, such as at least 150 ppm, such as at least 500 ppm (calculated as total compound) based on total weight of the sealing composition, and in some instances, no more than 30000 ppm, such as no more than 2000 ppm, such as no more than 1500 ppm (calculated as total compound) based on total weight of the sealing composition.
- the metal salts of the sealing composition i.e., the salts of lithium, Group IA metals other than lithium, Group VB, and/or Group VIB
- each may be present in the sealing composition in an amount of 25 ppm to 30000 ppm, such as 150 ppm to 2000 ppm, such as 500 ppm to 1500 (calculated as total compound) based on total weight of the sealing composition.
- the lithium cation, the Group IA cation other than lithium, the Group VB metal cation, and the Group VIB metal cation each may be present in the sealing composition in an amount of at least 5 ppm, such as at least 50 ppm, such as at least 150 ppm, such as at least 250 ppm (calculated as cation) based on total weight of the sealing composition, and in some instances, may be present in an amount of no more than 5500 ppm, such as no more than 1200 ppm, such as no more than 1000 ppm, such as no more than 500 ppm, (calculated as cation) based on total weight of the sealing composition.
- the lithium cation, the Group IA cation other than lithium, the Group VB metal cation, and the Group VIB metal cation each may be present in the sealing composition in an amount of 5 ppm to 5500 ppm, such as 50 ppm to 1000 ppm, (calculated as cation) based on total weight of the sealing composition, such as 150 ppm to 500 ppm.
- the lithium salt of the present invention may comprise an inorganic lithium salt, an organic lithium salt, or combinations thereof.
- the anion and the cation of the lithium salt both may be soluble in water.
- the lithium salt may have a solubility constant in water at a temperature of 25° C. (K; 25° C.) of at least 1 ⁇ 10 ⁇ 11 , such as least 1 ⁇ 10 ⁇ 4 , and in some instances, may be no more than 5 ⁇ 10 +2 .
- the lithium salt may have a solubility constant in water at a temperature of 25° C.
- solubility constant means the product of the equilibrium concentrations of the ions in a saturated aqueous solution of the respective lithium salt. Each concentration is raised to the power of the respective coefficient of ion in the balanced equation.
- solubility constants for various salts can be found in the Handbook of Chemistry and Physics.
- the sealing composition of the present invention may an include oxidizing agent, such as hydrogen peroxide, persulfates, perchlorates, sparged oxygen, bromates, peroxi-benzoates, ozone, and the like, or combinations thereof.
- the sealing composition may comprise 0.1 wt % to 15 wt % of an oxidizing agent based on total weight of the sealing composition, such as 2 wt % to 10 wt %, such as 6 wt % to 8 wt %.
- the sealing composition may be substantially free, or in some cases, essentially free, or in some cases, completely free, of an oxidizing agent.
- the sealing composition may exclude Group IIA metal cations or Group IIA metal-containing compounds, including but not limited to calcium.
- Non-limiting examples of such materials include Group IIA metal hydroxides, Group IIA metal nitrates, Group IIA metal halides, Group IIA metal sulfamates, Group IIA metal sulfates, Group IIA carbonates and/or Group IIA metal carboxylates.
- a sealing composition and/or a coating or a layer, respectively, formed from the same is substantially free, essentially free, or completely free of a Group IIA metal cation, this includes Group IIA metal cations in any form, such as, but not limited to, the Group IIA metal-containing compounds listed above.
- the sealing composition may exclude chromium or chromium-containing compounds.
- chromium-containing compound refers to materials that include hexavalent chromium. Non-limiting examples of such materials include chromic acid, chromium trioxide, chromic acid anhydride, dichromate salts, such as ammonium dichromate, sodium dichromate, potassium dichromate, and calcium, barium, magnesium, zinc, cadmium, and strontium dichromate.
- chromium in any form, such as, but not limited to, the hexavalent chromium-containing compounds listed above.
- the present sealing compositions and/or coatings or layers, respectively, deposited from the same may be substantially free, may be essentially free, and/or may be completely free of one or more of any of the elements or compounds listed in the preceding paragraph.
- a sealing composition and/or coating or layer, respectively, formed from the same that is substantially free of chromium or derivatives thereof means that chromium or derivatives thereof are not intentionally added, but may be present in trace amounts, such as because of impurities or unavoidable contamination from the environment.
- the amount of material is so small that it does not affect the properties of the sealing composition; in the case of chromium, this may further include that the element or compounds thereof are not present in the sealing compositions and/or coatings or layers, respectively, formed from the same in such a level that it causes a burden on the environment.
- the term “substantially free” means that the sealing compositions and/or coating or layers, respectively, formed from the same contain less than 10 ppm of any or all of the elements or compounds listed in the preceding paragraph, based on total weight of the composition or the layer, respectively, if any at all.
- the term “essentially free” means that the sealing compositions and/or coatings or layers, respectively, formed from the same contain less than 1 ppm of any or all of the elements or compounds listed in the preceding paragraph, if any at all.
- the term “completely free” means that the sealing compositions and/or coatings or layers, respectively, formed from the same contain less than 1 ppb of any or all of the elements or compounds listed in the preceding paragraph, if any at all.
- the sealing composition may, in some instances, exclude phosphate ions or phosphate-containing compounds and/or the formation of sludge, such as aluminum phosphate, iron phosphate, and/or zinc phosphate, formed in the case of using a treating agent based on zinc phosphate.
- phosphate-containing compounds include compounds containing the element phosphorous such as ortho phosphate, pyrophosphate, metaphosphate, tripolyphosphate, organophosphonates, and the like, and can include, but are not limited to, monovalent, divalent, or trivalent cations such as: sodium, potassium, calcium, zinc, nickel, manganese, aluminum and/or iron.
- a composition and/or a layer or coating comprising the same is substantially free, essentially free, or completely free of phosphate, this includes phosphate ions or compounds containing phosphate in any form.
- sealing composition and/or layers deposited from the same may be substantially free, or in some cases may be essentially free, or in some cases may be completely free, of one or more of any of the ions or compounds listed in the preceding paragraph.
- a sealing composition and/or layers deposited from the same that is substantially free of phosphate means that phosphate ions or compounds containing phosphate are not intentionally added, but may be present in trace amounts, such as because of impurities or unavoidable contamination from the environment. In other words, the amount of material is so small that it does not affect the properties of the composition; this may further include that phosphate is not present in the sealing compositions and/or layers deposited from the same in such a level that they cause a burden on the environment.
- substantially free means that the sealing compositions and/or layers deposited from the same contain less than 5 ppm of any or all of the phosphate anions or compounds listed in the preceding paragraph, based on total weight of the composition or the layer, respectively, if any at all.
- essentially free means that the sealing compositions and/or layers comprising the same contain less than 1 ppm of any or all of the phosphate anions or compounds listed in the preceding paragraph.
- completely free means that the sealing compositions and/or layers comprising the same contain less than 1 ppb of any or all of the phosphate anions or compounds listed in the preceding paragraph, if any at all.
- the sealing composition may, in some instances, exclude fluoride or fluoride sources.
- fluoride sources include monofluorides, bifluorides, fluoride complexes, and mixtures thereof known to generate fluoride ions.
- a composition and/or a layer or coating comprising the same is substantially free, essentially free, or completely free of fluoride, this includes fluoride ions or fluoride sources in any form, but does not include unintentional fluoride that may be present in a bath as a result of, for example, carry-over from prior treatment baths in the processing line, municipal water sources (e.g.: fluoride added to water supplies to prevent tooth decay), fluoride from a pretreated substrate, or the like.
- a bath that is substantially free, essentially free, or completely free of fluoride may have unintentional fluoride that may be derived from these external sources, even though the composition used to make the bath prior to use on the processing line was substantially free, essentially free, or completely free of fluoride.
- the sealing composition may be substantially free of any fluoride-sources, such as ammonium and alkali metal fluorides, acid fluorides, fluoroboric, fluorosilicic, fluorotitanic, and fluorozirconic acids and their ammonium and alkali metal salts, and other inorganic fluorides, nonexclusive examples of which are: zinc fluoride, zinc aluminum fluoride, titanium fluoride, zirconium fluoride, nickel fluoride, ammonium fluoride, sodium fluoride, potassium fluoride, and hydrofluoric acid, as well as other similar materials known to those skilled in the art.
- fluoride-sources such as ammonium and alkali metal fluorides, acid fluorides, fluoroboric, fluorosilicic, fluorotitanic, and fluorozirconic acids and their ammonium and alkali metal salts, and other inorganic fluorides, nonexclusive examples of which are: zinc fluoride, zinc aluminum fluoride, titanium flu
- Fluoride present in the sealing composition that is not bound to metals ions such as Group IVB metal ions, or hydrogen ion, defined herein as “free fluoride,” may be measured as an operational parameter in the sealing composition bath using, for example, an Orion Dual Star Dual Channel Benchtop Meter equipped with a fluoride ion selective electrode (“ISE”) available from Thermoscientific, the Symphony® Fluoride Ion Selective Combination Electrode supplied by VWR International, or similar electrodes. See, e.g., Light and Cappuccino, Determination of fluoride in toothpaste using an ion - selective electrode , J. Chem. Educ., 52:4, 247-250, April 1975.
- ISE fluoride ion selective electrode
- the fluoride ISE may be standardized by immersing the electrode into solutions of known fluoride concentration and recording the reading in millivolts, and then plotting these millivolt readings in a logarithmic graph. The millivolt reading of an unknown sample can then be compared to this calibration graph and the concentration of fluoride determined.
- the fluoride ISE can be used with a meter that will perform the calibration calculations internally and thus, after calibration, the concentration of the unknown sample can be read directly.
- Fluoride ion is a small negative ion with a high charge density, so in aqueous solution it is frequently complexed with metal ions having a high positive charge density, such as Group IVB metal ions, or with hydrogen ion. Fluoride anions in solution that are ionically or covalently bound to metal cations or hydrogen ion are defined herein as “bound fluoride.” The fluoride ions thus complexed are not measurable with the fluoride ISE unless the solution they are present in is mixed with an ionic strength adjustment buffer (e.g.: citrate anion or EDTA) that releases the fluoride ions from such complexes.
- an ionic strength adjustment buffer e.g.: citrate anion or EDTA
- total fluoride can be calculated by comparing the weight of the fluoride supplied in the sealer composition by the total weight of the composition.
- the treatment composition may, in some instances, be substantially free, or in some instances, essentially free, or in some instances, completely free, of cobalt ions or cobalt-containing compounds.
- cobalt-containing compounds include compounds, complexes or salts containing the element cobalt such as, for example, cobalt sulfate, cobalt nitrate, cobalt carbonate and cobalt acetate.
- cobalt ions or compounds containing cobalt in any form.
- the treatment composition may, in some instances, be substantially free, or in some instances, essentially free, or in some instances, completely free, of vanadium ions or vanadium-containing compounds.
- vanadium-containing compounds include compounds, complexes or salts containing the element vanadium such as, for example, vanadates and decavanadates that include counterions of alkali metal or ammonium cations, including, for example, sodium ammonium decavanadate.
- a composition and/or a layer or coating comprising the same is substantially free, essentially free, or completely free of vanadium, this includes vanadium ions or compounds containing vanadium in any form.
- the sealing composition may optionally further contain an indicator compound, so named because it indicates, for example, the presence of a chemical species, such as a metal ion, the pH of a composition, and the like.
- an “indicator”, “indicator compound”, and like terms as used herein refer to a compound that changes color in response to some external stimulus, parameter, or condition, such as the presence of a metal ion, or in response to a specific pH or range of pHs.
- the indicator compound used according to the present invention can be any indicator known in the art that indicates the presence of a species, a particular pH, and the like.
- a suitable indicator may be one that changes color after forming a metal ion complex with a particular metal ion.
- the metal ion indicator is generally a highly conjugated organic compound.
- the indicator compound can be one in which the color changes upon change of the pH; for example, the compound may be one color at an acidic or neutral pH and change color in an alkaline pH, or vice versa.
- Such indicators are well known and widely commercially available.
- An indicator that “changes color upon transition from a first pH to a second pH” i.e., from a first pH to a second pH that is more or less acidic or alkaline) therefore has a first color (or is colorless) when exposed to a first pH and changes to a second color (or goes from colorless to colored) upon transition to a second pH (i.e., one that is either more or less acidic or alkaline than the first pH).
- an indicator that “changes color upon transition to a more alkaline pH (or less acidic pH) goes from a first color/colorless to a second color/color when the pH transitions from acidic/neutral to alkaline.
- an indicator that “changes color upon transition to a more acidic pH (or less alkaline pH) goes from a first color/colorless to a second color/color when the pH transitions from alkaline/neutral to acidic.
- Non-limiting examples of such indicator compounds include methyl orange, xylenol orange, catechol violet, bromophenol blue, green and purple, eriochrome black T, Celestine blue, hematoxylin, calmagite, gallocyanine, and combinations thereof.
- the indicator compound may comprise an organic indicator compound that is a metal ion indicator.
- Nonlimiting examples of indicator compounds include those found in Table 1. Fluorescent indicators, which will emit light in certain conditions, can also be used according to the present invention, although the use of a fluorescent indicator also may be specifically excluded. That is, alternatively, conjugated compounds that exhibit fluorescence are specifically excluded.
- fluorescent indicator and like terms refer to compounds, molecules, pigments, and/or dyes that will fluoresce or otherwise exhibit color upon exposure to ultraviolet or visible light. To “fluoresce” will be understood as emitting light following absorption of shorter wavelength light or other electromagnetic radiation.
- tags examples include acridine, anthraquinone, coumarin, diphenylmethane, diphenylnaphthlymethane, quinoline, stilbene, triphenylmethane, anthracine and/or molecules containing any of these moieties and/or derivatives of any of these such as rhodamines, phenanthridines, oxazines, fluorones, cyanines and/or acridines.
- the conjugated compound useful as indicator may for example comprise catechol violet, as shown in Table 1.
- Catechol violet (CV) is a sulfone phthalein dye made from condensing two moles of pyrocatechol with one mole of o-sulfobenzoic acid anhydride. It has been found that CV has indicator properties and when incorporated into compositions having metal ions, it forms complexes, making it useful as a complexiometric reagent. As the composition containing the CV chelates metal ions coming from the metal substrate (i.e., those having bi- or higher valence), a generally blue to blue-violet color is observed.
- Xylenol orange as shown in Table 1 may likewise be employed in the compositions according to the present invention. It has been found that xylenol orange has metal ion (i.e., those having bi- or higher valence) indicator properties and when incorporated into compositions having metal ions, it forms complexes, making it useful as a complexiometric reagent. As the composition containing the xylenol orange chelates metal ions, a solution of xylenol orange turns from red to a generally blue color.
- the indicator compound may be present in the sealing composition in an amount of at least 0.01 g/1000 g sealing composition, such as at least 0.05 g/1000 g sealing composition, and in some instances, no more than 3 g/1000 g sealing composition, such as no more than 0.3 g/1000 g sealing composition. According to the present invention, the indicator compound may be present in the sealing composition in an amount of 0.01 g/1000 g sealing composition to 3 g/1000 g sealing composition, such as 0.05 g/1000 g sealing composition to 0.3 g/1000 g sealing composition.
- the indicator compound changing color in response to a certain external stimulus provides a benefit when using the sealing composition in that it can serve, for example, as a visual indication that a substrate has been treated with the composition.
- a sealing composition comprising an indicator that changes color when exposed to a metal ion that is present in the substrate will change color upon complexing with metal ions in that substrate; this allows the user to see that the substrate has been contacted with the composition.
- Similar benefits can be realized by depositing an alkaline or acid layer on a substrate and contacting the substrate with a composition of the present invention that changes color when exposed to an alkaline or acidic pH.
- the sealing composition of the present invention may further comprise a nitrogen-containing heterocyclic compound.
- the nitrogen-containing heterocyclic compound may include cyclic compounds having 1 nitrogen atom, such as pyrroles, and azole compounds having 2 or more nitrogen atoms, such as pyrazoles, imidazoles, triazoles, tetrazoles and pentazoles, 1 nitrogen atom and 1 oxygen atom, such as oxazoles and isoxazoles, or 1 nitrogen atom and 1 sulfur atom, such as thiazoles and isothiazoles.
- Nonlimiting examples of suitable azole compounds include 2,5-dimercapto-1,3,4-thiadiazole (CAS: 1072-71-5), 1H-benzotriazole (CAS: 95-14-7), 1H-1,2,3-triazole (CAS: 288-36-8), 2-amino-5-mercapto-1,3,4-thiadiazole (CAS: 2349-67-9), also named 5-amino-1,3,4-thiadiazole-2-thiol, and 2-amino-1,3,4-thiadiazole (CAS: 4005-51-0).
- the azole compound comprises 2,5-dimercapto-1,3,4-thiadiazole.
- the nitrogen-containing heterocyclic compound may be in the form of a salt, such as a sodium salt.
- the nitrogen-containing heterocyclic compound may be present in the sealing composition at a concentration of at least 0.0005 g per liter of composition, such as at least 0.0008 g per liter of composition, such as at least 0.002 g per liter of composition, and in some instances, may be present in the sealing composition in an amount of no more than 3 g per liter of composition, such as no more than 0.2 g per liter of composition, such as no more than 0.1 g per liter of composition.
- the nitrogen-containing heterocyclic compound may be present in the sealing composition (if at all) at a concentration of 0.0005 g per liter of composition to 3 g per liter of composition, such as 0.0008 g per liter of composition to 0.2 g per liter of composition, such as 0.002 g per liter of composition to 0.1 g per liter of composition.
- the sealing composition may comprise an aqueous medium and optionally may contain other materials such as at least one organic solvent.
- suitable such solvents include propylene glycol, ethylene glycol, glycerol, low molecular weight alcohols, and the like.
- the organic solvent may be present in the sealing composition in an amount of at least 1 g solvent per liter of sealing composition, such as at least about 2 g solvent per liter of sealing solution, and in some instances, may be present in an amount of no more than 40 g solvent per liter of sealing composition, such as no more than 20 g solvent per liter of sealing solution.
- the organic solvent may be present in the sealing composition, if at all, in an amount of 1 g solvent per liter of sealing composition to 40 g solvent per liter of sealing composition, such as 2 g solvent per liter of sealing composition to 20 g solvent per liter of sealing composition.
- the pH of the sealing composition may be at least 9.5, such as at least 10, such as at least 11, and in some instances may be no higher than 12.5, such as no higher than 12, such as no higher than 11.5.
- the pH of the sealing composition may be 9.5 to 12.5, such as 10 to 12, such as 11 to 11.5.
- the pH of the sealing composition may be adjusted using, for example, any acid and/or base as is necessary.
- the pH of the sealing composition may be maintained through the inclusion of an acidic material, including carbon dioxide, water soluble and/or water dispersible acids, such as nitric acid, sulfuric acid, and/or phosphoric acid.
- the pH of the sealing composition may be maintained through the inclusion of a basic material, including water soluble and/or water dispersible bases, including carbonates such as Group I carbonates, Group II carbonates, hydroxides such as sodium hydroxide, potassium hydroxide, or ammonium hydroxide, ammonia, and/or amines such as triethylamine, methylethyl amine, or mixtures thereof.
- a basic material including water soluble and/or water dispersible bases, including carbonates such as Group I carbonates, Group II carbonates, hydroxides such as sodium hydroxide, potassium hydroxide, or ammonium hydroxide, ammonia, and/or amines such as triethylamine, methylethyl amine, or mixtures thereof.
- the sealing composition may comprise a carrier, often an aqueous medium, so that the composition is in the form of a solution or dispersion of the lithium cation in the carrier.
- the solution or dispersion may be brought into contact with the substrate by any of a variety of known techniques, such as dipping or immersion, spraying, intermittent spraying, dipping followed by spraying, spraying followed by dipping, brushing, or roll-coating.
- the solution or dispersion when applied to the metal substrate may be at a temperature ranging from 40° F. to about 160° F., such as 60° F. to 110° F.
- the process of contacting the metal substrate with the sealing composition may be carried out at ambient or room temperature.
- the contact time is often from about 1 second to about 15 minutes, such as about 5 seconds to about 2 minutes.
- the substrate optionally may be air dried at room temperature or may be dried with hot air, for example, by using an air knife, by flashing off the water by brief exposure of the substrate to a high temperature, such as by drying the substrate in an oven at 15° C. to 100° C., such as 20° C. to 90° C., or in a heater assembly using, for example, infrared heat, such as for 10 minutes at 70° C., or by passing the substrate between squeegee rolls.
- the substrate surface may be partially, or in some instances, completely dried prior to any subsequent contact of the substrate surface with any water, solutions, compositions, or the like.
- “completely dry” or “completely dried” means there is no moisture on the substrate surface visible to the human eye.
- the substrate optionally is not rinsed or contacted with any aqueous solutions prior to contacting at least a portion of the substrate surface with subsequent treatment compositions to form films, layers, and/or coatings thereon (described below).
- the substrate optionally may be contacted with tap water, deionized water, RO water and/or any aqueous solution known to those of skill in the art of substrate treatment, wherein such water or aqueous solution may be at a temperature of room temperature (60° F.) to 212° F.
- the substrate then optionally may be dried, for example air dried or dried with hot air as described in the preceding paragraph such that the substrate surface may be partially, or in some instances, completely dried prior to any subsequent contact of the substrate surface with any water, solutions, compositions, or the like.
- the thickness of the layer formed by the treatment composition may for instance be up to 550 nm, such as 5 nm to 550 nm, such as 10 nm to 400 nm, such as 25 nm to 250 nm. Thickness of layer formed from the treatment composition can be determined using a handful of analytical techniques including, but not limited to XPS (x-ray photoelectron spectroscopy) depth profiling or TEM (transmission electron microscopy).
- XPS x-ray photoelectron spectroscopy
- TEM transmission electron microscopy
- thickness when used with respect to a layer formed by the treatment composition of the present invention, refers to either (a) a layer formed above the original air/substrate interface, (b) a modified layer formed below the pretreatment/substrate interface, or (c) a combination of (a) and (b), as illustrated in FIG. 1 .
- modified layer (b) is shown extending to the pretreatment/substrate interface in FIG. 1 , an intervening layer may be present between the modified layer (b) and the pretreatment/substrate interface.
- a combination of (a) and (b) is not limited to a continuous layer and may include multiple layers with intervening layers therebetween, and the measurement of the thickness of layer (c) may exclude the intervening layers.
- the substrate having the layer formed from the sealing composition may have at least a 50% reduction in the number of pits on the substrate surface compared to a substrate that does not have a layer formed from the sealing composition thereon following 3 day exposure in neutral salt spray cabinet operated according to ASTM B117.
- the substrate having the layer formed from the sealing composition may have at least a 50% reduction in the number of pits on the substrate surface compared to a substrate that does not have a layer formed from the sealing composition thereon following 7 day exposure in neutral salt spray cabinet operated according to ASTM B117.
- At least a portion of the substrate surface may be cleaned and/or deoxidized prior to contacting at least a portion of the substrate surface with a sealing composition described above, in order to remove grease, dirt, and/or other extraneous matter.
- At least a portion of the surface of the substrate may be cleaned by physical and/or chemical means, such as mechanically abrading the surface and/or cleaning/degreasing the surface with commercially available alkaline or acidic cleaning agents that are well known to those skilled in the art.
- alkaline cleaners suitable for use in the present invention include ChemkleenTM 166HP, 166M/C, 177, 490MX, 2010LP, and Surface Prep 1 (SPI), Ultrax 32, Ultrax 97, Ultrax 29, and Ultrax92D, each of which are commercially available from PPG Industries, Inc. (Cleveland, Ohio), and any of the DFM Series, RECC 1001, and 88X1002 cleaners commercially available from PRC-DeSoto International, Sylmar, Calif.), and Turco 4215-NCLT and Ridolene (commercially available from Henkel Technologies, Madison Heights, Mich.). Such cleaners are often preceded or followed by a water rinse, such as with tap water, distilled water, or combinations thereof.
- a water rinse such as with tap water, distilled water, or combinations thereof.
- the cleaned substrate surface may be deoxidized, mechanically and/or chemically.
- the term “deoxidize” means removal of the oxide layer found on the surface of the substrate in order to promote uniform deposition of the conversion composition (described below), as well as to promote the adhesion of the conversion composition coating to the substrate surface.
- Suitable deoxidizers will be familiar to those skilled in the art.
- a typical mechanical deoxidizer may be uniform roughening of the substrate surface, such as by using a scouring or cleaning pad.
- Typical chemical deoxidizers include, for example, acid-based deoxidizers such as phosphoric acid, nitric acid, fluoroboric acid, sulfuric acid, chromic acid, hydrofluoric acid, and ammonium bifluoride, or Amchem 7/17 deoxidizers (available from Henkel Technologies, Madison Heights, Mich.), OAKITE DEOXIDIZER LNC (commercially available from Chemetall), TURCO DEOXIDIZER 6 (commercially available from Henkel), or combinations thereof.
- acid-based deoxidizers such as phosphoric acid, nitric acid, fluoroboric acid, sulfuric acid, chromic acid, hydrofluoric acid, and ammonium bifluoride, or Amchem 7/17 deoxidizers (available from Henkel Technologies, Madison Heights, Mich.), OAKITE DEOXIDIZER LNC (commercially available from Chemetall), TURCO DEOXIDIZER 6 (commercially available from Henkel), or combinations thereof.
- the chemical deoxidizer comprises a carrier, often an aqueous medium, so that the deoxidizer may be in the form of a solution or dispersion in the carrier, in which case the solution or dispersion may be brought into contact with the substrate by any of a variety of known techniques, such as dipping or immersion, spraying, intermittent spraying, dipping followed by spraying, spraying followed by dipping, brushing, or roll-coating.
- a temperature range of the solution or dispersion when applied to the metal substrate, based on etch rates, for example, at a temperature ranging from 50° F. to 150° F. (10° C. to 66° C.), such as from 70° F. to 130° F.
- the contact time may be from 30 seconds to 20 minutes, such as 1 minute to 15 minutes, such as 90 seconds to 12 minutes, such as 3 minutes to 9 minutes.
- the substrate optionally may be rinsed with tap water, deionized water, and/or an aqueous solution of rinsing agents in order to remove any residue.
- the wet substrate surface may be treated with a conversion composition (described below) and/or a sealing composition (described above), or the substrate may be dried prior to treating the substrate surface, such as air dried, for example, by using an air knife, by flashing off the water by brief exposure of the substrate to a high temperature, such as 15° C. to 100° C., such as 20° C. to 90° C., or in a heater assembly using, for example, infrared heat, such as for 10 minutes at 70° C., or by passing the substrate between squeegee rolls.
- a conversion composition described below
- a sealing composition described above
- the substrate may be dried prior to treating the substrate surface, such as air dried, for example, by using an air knife, by flashing off the water by brief exposure of the substrate to a high temperature, such as 15° C. to 100
- the substrate surface optionally may be contacted with a conversion composition prior to or after being contacted with the sealing composition described above.
- the conversion composition may be spontaneously depositable or electrodepositable.
- spontaneously depositable when used with respect to the conversion composition, refers to a composition that is capable of reacting with and chemically altering the substrate surface and binding to it to form a protective layer in the absence of an externally applied voltage.
- an “electrodepositable,” when used with respect to the conversion composition refers to a composition containing a non-elemental metal, i.e.
- an electrodepositable conversion composition may be applied using any methods or parameters known to those skilled in the art.
- the conversion composition may comprise a lanthanide series element cation, a Group IIIB metal cation and/or a Group IVB metal cation.
- the conversion composition also may further comprise an ion of a Group IIA metal, a Group VB metal, a Group VIB metal, a Group VIIB metal, and/or a Group XII metal (together with the lanthanide series cation, the Group IIIB metal cation, and/or the Group IVB metal cation, referred to collectively herein as “conversion composition metal cations”).
- the salts of the conversion composition metal cations may be present in the conversion composition in an amount of at least 5 ppm, such as at least 50 ppm, such as at least 100 ppm, (calculated as metal salt) based on total weight of the conversion composition, and in some instances, may be present in an amount of no more than 25000 ppm, such as no more than 9000 ppm, such as no more than 1500 (calculated as metal salt) based on total weight of the conversion composition.
- the salt of the conversion composition metal cations may be present in the conversion composition in an amount of 5 ppm to 25000 ppm (calculated as metal salt) based on total weight of the conversion composition, such as 50 ppm to 9000 ppm, such as 100 ppm to 1500 ppm.
- the conversion composition metal cation may be present in the conversion composition in an amount of at least 5 ppm, such as at least 150 ppm, such as at least 300 ppm, (calculated as metal cation) based on total weight of the conversion composition, and in some instances may be present in the conversion composition in an amount of no more than 25,000 ppm, such as no more than 12,500 ppm, such as no more than 10,000 ppm, (calculated as metal cation) based on total weight of the conversion composition.
- the conversion composition metal cation may be present in the conversion composition in an amount of 5 ppm to 25,000 ppm, such as 150 ppm to 12,500 ppm, such as 300 ppm to 10,000 ppm, (calculated as metal cation) based on total weight of the conversion composition.
- the lanthanide series element cation may, for example, comprise cerium, praseodymium, terbium, or combinations thereof; the Group IIA metal cation may comprise magnesium; the Group IIIB metal cation may comprise yttrium, scandium, or combinations thereof; the Group IVB metal cation may comprise zirconium, titanium, hafnium, or combinations thereof; the Group VB metal cation may comprise vanadium; the Group VIB metal may comprise molybdenum; the Group VIIB metal cation may comprise trivalent or hexavalent chromium or manganese; and the Group XII metal cation may comprise zinc.
- the Group IIIB metal and/or Group IVB metal cation used in the conversion composition may be a compound of zirconium, titanium, hafnium, yttrium, scandium, or a mixture thereof.
- Suitable compounds of zirconium include, but are not limited to, hexafluorozirconic acid, alkali metal and ammonium salts thereof, ammonium zirconium carbonate, zirconyl nitrate, zirconyl sulfate, zirconium carboxylates and zirconium hydroxy carboxylates, such as zirconium acetate, zirconium oxalate, ammonium zirconium glycolate, ammonium zirconium lactate, ammonium zirconium citrate, and mixtures thereof.
- Suitable compounds of titanium include, but are not limited to, fluorotitanic acid and its salts.
- a suitable compound of hafnium includes, but is not limited to, hafnium nitrate.
- Suitable compounds of yttrium include, but are not limited to, yttrium halides.
- the Group IIIB metal cation and/or the Group IVB metal cation may be present in the conversion composition in a total amount of at least 20 ppm metal (calculated as metal cation), based on total weight of the conversion composition, such as at least 50 ppm metal, or, in some cases, at least 70 ppm metal.
- the Group IIIB metal cation and/or the Group IVB metal cation may be present in the conversion composition in a total amount of no more than 1000 ppm metal (calculated as metal cation), based on total weight of the conversion composition, such as no more than 600 ppm metal, or, in some cases, no more than 300 ppm metal.
- the Group IIIB metal cation and/or the Group IVB metal cation may be present in the conversion composition in a total amount of 20 ppm metal to 1000 ppm metal (calculated as metal cation), based on total weight of the conversion composition, such as from 50 ppm metal to 600 ppm metal, such as from 70 ppm metal to 300 ppm metal.
- total amount when used with respect to the amount of Group IIIB metal cation and/or Group IVB metal cation, means the sum of all Group IIIB and/or Group IV metal cations present in the conversion composition.
- the salts of the conversion composition metal cations may be present in the conversion composition in an amount of at least 5 ppm, such as at least 50 ppm, such as at least 100 ppm, (calculated as metal salt) based on total weight of the conversion composition, and in some instances, may be present in an amount of no more than 25000 ppm, such as no more than 9000 ppm, such as no more than 1500 (calculated as total metal salt) based on total weight of the conversion composition.
- the salt of the conversion composition metal cations may be present in the conversion composition in an amount of 5 ppm to 25000 ppm, such as 50 ppm to 9000 ppm, such as 100 ppm to 1500 ppm.
- the conversion composition metal cation may be present in the conversion composition in an amount of at least 5 ppm, such as at least 150 ppm, such as at least 300 ppm, (calculated as metal cation) based on total weight of the conversion composition, and in some instances may be present in the conversion composition in an amount of no more than 25,000 ppm, such as no more than 12,500 ppm, such as no more than 10,000 ppm, (calculated as metal cation) based on total weight of the conversion composition.
- the conversion composition metal cation may be present in the conversion composition in an amount of 5 ppm to 25,000 ppm, such as 150 ppm to 12,500 ppm, such as 300 ppm to 10,000 ppm (calculated as metal cation) based on total weight of the conversion composition.
- the conversion composition also may comprise an electropositive metal ion.
- electropositive metal ion refers to metal ions that will be reduced by the metal substrate being treated when the conversion solution contacts the surface of the metallic substrate.
- the reduction potential is expressed in volts, and is measured relative to the standard hydrogen electrode, which is arbitrarily assigned a reduction potential of zero.
- the reduction potential for several elements is set forth in Table 2 below (according to the CRC 82 nd Edition, 2001-2002). An element or ion is more easily reduced than another element or ion if it has a voltage value, E*, in the following table, that is more positive than the elements or ions to which it is being compared.
- the metal substrate comprises one of the materials listed earlier, such as cold rolled steel, hot rolled steel, steel coated with zinc metal, zinc compounds, or zinc alloys, hot-dipped galvanized steel, galvanealed steel, steel plated with zinc alloy, aluminum alloys, aluminum plated steel, aluminum alloy plated steel, magnesium and magnesium alloys
- suitable electropositive metals for deposition thereon include, for example, nickel, copper, silver, and gold, as well mixtures thereof.
- both soluble and insoluble compounds may serve as a source of copper ions in the conversion compositions.
- the supplying source of copper ions in the conversion composition may be a water soluble copper compound.
- Specific examples of such compounds include, but are not limited to, copper cyanide, copper potassium cyanide, copper sulfate, copper nitrate, copper pyrophosphate, copper thiocyanate, disodium copper ethylenediaminetetraacetate tetrahydrate, copper bromide, copper oxide, copper hydroxide, copper chloride, copper fluoride, copper gluconate, copper citrate, copper lauroyl sarcosinate, copper formate, copper acetate, copper propionate, copper butyrate, copper lactate, copper oxalate, copper phytate, copper tartrate, copper malate, copper succinate, copper malonate, copper maleate, copper benzoate, copper salicylate, copper aspartate, copper glutamate, copper fum
- the copper compound may be added as a copper complex salt such as K 3 Cu(CN) 4 or Cu-EDTA, which can be present stably in the conversion composition on its own, but it is also possible to form a copper complex that can be present stably in the conversion composition by combining a complexing agent with a compound that is difficult to solubilize on its own.
- a copper cyanide complex formed by a combination of CuCN and KCN or a combination of CuSCN and KSCN or KCN
- a Cu-EDTA complex formed by a combination of CuSO 4 and EDTA.2Na examples thereof include a copper cyanide complex formed by a combination of CuCN and KCN or a combination of CuSCN and KSCN or KCN, and a Cu-EDTA complex formed by a combination of CuSO 4 and EDTA.2Na.
- a compound that can form a complex with copper ions can be used; examples thereof include inorganic compounds such as cyanide compounds and thiocyanate compounds, and polycarboxylic acids, and specific examples thereof include ethylenediaminetetraacetic acid, salts of ethylenediaminetetraacetic acid such as dihydrogen disodium ethylenediaminetetraacetate dihydrate, aminocarboxylic acids such as nitrilotriacetic acid and iminodiacetic acid, oxycarboxylic acids such as citric acid and tartaric acid, succinic acid, oxalic acid, ethylenediaminetetramethylenephosphonic acid, and glycine, and organophosphonates such as 1-hydroxethylidene-1,1-diphosphonic acid (commercially available from Italmatch Chemicals as Dequest 2010).
- inorganic compounds such as cyanide compounds and thiocyanate compounds
- polycarboxylic acids and specific examples thereof include ethylenediaminet
- the electropositive metal ion may be present in the conversion composition in an amount of at least 2 ppm (calculated as metal ion) based on the total weight of the conversion composition, such as at least 4 ppm, such as at least 6 ppm, such as at least 8 ppm, such as at least 10 ppm.
- the electropositive metal ion may be present in the conversion composition in an amount of no more than 100 ppm (calculated as metal ion) based on the total weight of the conversion composition, such as no more than 80 ppm, such as no more than 60 ppm, such as no more than 40 ppm, such as no more than 20 ppm.
- the electropositive metal ion may be present in the conversion composition in an amount of from 2 ppm to 100 ppm (calculated as metal ion) based on the total weight of the conversion composition, such as from 4 ppm to 80 ppm, such as from 6 ppm to 60 ppm, such as from 8 ppm to 40 ppm, such as from 10 ppm to 20 ppm.
- the amount of electropositive metal ion in the conversion composition can range between the recited values inclusive of the recited values.
- a source of fluoride may be present in the conversion composition.
- the amount of fluoride disclosed or reported in the conversion composition is referred to as “free fluoride,” as measured in part per millions of fluoride. Free fluoride is defined above as being able to be measured by a fluoride-selective ISE.
- a conversion may also contain “bound fluoride, which is described above. The sum of the concentrations of the bound and free fluoride equal the total fluoride, which can be determined as described above.
- the total fluoride in the conversion composition can be supplied by hydrofluoric acid, as well as alkali metal and ammonium fluorides or hydrogen fluorides.
- total fluoride in the conversion composition may be derived from Group IVB metals present in the conversion composition, including, for example, hexafluorozirconic acid or hexafluorotitanic acid.
- Other complex fluorides such as H 2 SiF 6 or HBF 4 , can be added to the conversion composition to supply total fluoride.
- the skilled artisan will understand that the presence of free fluoride in the conversion bath can impact conversion deposition and etching of the substrate, hence it is critical to measure this bath parameter.
- the levels of free fluoride will depend on the pH and the addition of chelators into the conversion bath and indicates the degree of fluoride association with the metal ions/protons present in the conversion bath. For example, conversion compositions of identical total fluoride levels can have different free fluoride levels which will be influenced by the pH and chelators present in the conversion solution.
- the total fluoride of the conversion composition may be present in an amount of at least 25 ppm, based on a total weight of the conversion composition, such as at least 100 ppm fluoride, such as at least 200 ppm fluoride. According to the present invention, the total fluoride of the conversion composition may be present in an amount of no more than 5000 ppm, based on a total weight of the conversion composition, such as no more than 2000 ppm fluoride, such as no more than 1000 ppm fluoride.
- the total fluoride of the conversion composition may be present in an amount of 10 ppm fluoride to 5000 ppm fluoride, based on a total weight of the conversion composition, such as 100 ppm fluoride to 2000 ppm, such as no more than 200 ppm fluoride to 1000 ppm fluoride.
- the free fluoride of the conversion composition may be present in an amount of at least 15 ppm, based on a total weight of the conversion composition, such as at least 50 ppm free fluoride, such as at least 100 ppm free fluoride, such as at least 200 ppm free fluoride.
- the free fluoride of the conversion composition may be present in an amount of no more than 2500 ppm, based on a total weight of the conversion composition, such as no more than 1000 ppm free fluoride, such as no more than 500 ppm free fluoride, such as no more than 250 ppm free fluoride.
- the free fluoride of the conversion composition may be present in an amount of 15 ppm free fluoride to 2500 ppm free fluoride, based on a total weight of the conversion composition, such as 50 ppm fluoride to 1000 ppm, such as no more than 200 ppm free fluoride to 500 ppm free fluoride, such as no more than 100 ppm free fluoride to 250 ppm free fluoride.
- the conversion composition also may comprise a lithium cation.
- the conversion composition may further comprise an anion that may be suitable for forming a salt with the lithium cation.
- suitable lithium salts include lithium nitrate, lithium sulfate, lithium fluoride, lithium chloride, lithium hydroxide, lithium carbonate, lithium iodide, and combinations thereof.
- the lithium cation may be present in the conversion composition in an amount of at least 2 ppm (as lithium cation) based on a total weight of the conversion composition, such as at least 5 ppm, such as at least 25 ppm, such as at least 75 ppm, and in some instances, may be present in amount of no more than 500 ppm, based on a total weight of the conversion composition, such as no more than 250 ppm, such as no more than 125 ppm, such as no more than 100 ppm.
- the lithium cation may be present in the conversion composition in an amount of 2 ppm to 500 ppm (as lithium cation) based on a total weight of the conversion composition, such as 5 ppm to 250 ppm, such as 25 ppm to 125 ppm, such as 75 ppm to 100 ppm.
- the amount of lithium cation in the conversion composition can range between the recited values inclusive of the recited values.
- the conversion composition may also comprise a molybdenum cation.
- the conversion composition may further comprise an anion that may be suitable for forming a salt with the molybdenum cation.
- suitable molybdenum salts include sodium molybdate, calcium molybdate, potassium molybdate, ammonium molybdate, molybdenum chloride, molybdenum acetate, molybdenum sulfamate, molybdenum formate, molybdenum lactate, and combinations thereof.
- molybdenum cation may be present in the conversion composition in an amount of at least 5 ppm (as molybdenum cation) based on a total weight of the conversion composition, such as at least 25 ppm, such as 100 ppm, and in some instances, may be present in the conversion composition in an amount of no more than 500 ppm, based on total weight of the conversion composition, such as no more than 250 ppm, such as no more than 150 ppm.
- molybdenum may be present in the conversion composition in an amount of 5 ppm to 500 ppm (as molybdenum cation) based on total weight of the conversion composition, such as 25 ppm to 250 ppm, such as 100 ppm to 150 ppm.
- the amount of molybdenum in the conversion composition can range between the recited values inclusive of the recited values.
- the conversion composition may further comprise an anion that may be suitable for forming a salt with the conversion composition metal cations, such as a halogen, a nitrate, a sulfate, a phosphate, a silicate (orthosilicates and metasilicates), carbonates, hydroxides, and the like.
- the conversion composition metal salt may be present in the conversion composition in an amount of at least 50 ppm (calculated as metal salt) based on total weight of the conversion composition, such as at least 1000 ppm, and in some instances, may be present in an amount of no more than 30,000 ppm, such as no more than 2000 ppm.
- the conversion composition metal salt may be present in an amount of 50 ppm to 30,000 ppm, such as 1000 ppm to 2000 ppm (calculated as metal salt) based on total weight of the conversion composition.
- the halogen may be present in the conversion composition, if at all, in an amount of at least 5 ppm (calculated as anion) based on total weight of the conversion composition, such as at least 50 ppm, such as at least 150 ppm, such as at least 500 ppm, and may be present in an amount of no more than 25,000 ppm (calculated as anion) based on total weight of the conversion composition, such as no more than 18,500 ppm, such as no more than 4000 ppm, such as no more than 2000 ppm.
- the halogen may be present in the conversion composition, if at all, in an amount of 5 ppm to 25,000 ppm (calculated as anion) based on total weight of the conversion composition, such as 50 ppm to 18,500 ppm, such as 150 ppm to 4000, such as 500 ppm to 2000 ppm.
- the nitrate may be present in the conversion composition, if at all, in an amount of at least 2 ppm (calculated as anion) based on total weight of the conversion composition, such as at least 50 ppm, such as at least 250 ppm, and may be present in an amount of no more than 10,000 ppm (calculated as anion) based on total weight of the conversion composition, such as no more than 5000 ppm, such as no more than 2500 ppm.
- the halogen may be present in the conversion composition, if at all, in an amount of 2 ppm to 10,000 ppm (calculated as anion) based on total weight of the conversion composition, such as 50 ppm to 5000 ppm, such as 250 ppm to 2500 ppm.
- the conversion composition may, in some instances, comprise an oxidizing agent.
- oxidizing agent include peroxides, persulfates, perchlorates, hypochlorite, nitric acid, sparged oxygen, bromates, peroxi-benzoates, ozone, or combinations thereof.
- the oxidizing agent may be present, if at all, in an amount of at least 100 ppm, such as at least 500 ppm, based on total weight of the conversion composition, and in some instances, may be present in an amount of no more than 13,000 ppm, such as no more than 3000 ppm, based on total weight of the conversion composition. In some instances, the oxidizing agent may be present in the conversion composition, if at all, in an amount of 100 ppm to 13,000 ppm, such as 500 ppm to 3000 ppm, based on total weight of the conversion composition.
- the conversion composition may exclude chromium or chromium-containing compounds.
- chromium-containing compound refers to materials that include hexavalent chromium. Non-limiting examples of such materials include chromic acid, chromium trioxide, chromic acid anhydride, dichromate salts, such as ammonium dichromate, sodium dichromate, potassium dichromate, and calcium, barium, magnesium, zinc, cadmium, and strontium dichromate.
- chromium in any form, such as, but not limited to, the hexavalent chromium-containing compounds listed above.
- the present conversion compositions and/or coatings or layers, respectively, deposited from the same may be substantially free, may be essentially free, and/or may be completely free of one or more of any of the elements or compounds listed in the preceding paragraph.
- a conversion composition and/or coating or layer, respectively, formed from the same that is substantially free of chromium or derivatives thereof means that chromium or derivatives thereof are not intentionally added, but may be present in trace amounts, such as because of impurities or unavoidable contamination from the environment.
- the amount of material is so small that it does not affect the properties of the conversion composition; in the case of chromium, this may further include that the element or compounds thereof are not present in the conversion compositions and/or coatings or layers, respectively, formed from the same in such a level that it causes a burden on the environment.
- the term “substantially free” means that the conversion compositions and/or coating or layers, respectively, formed from the same contain less than 10 ppm of any or all of the elements or compounds listed in the preceding paragraph, based on total weight of the composition or the layer, respectively, if any at all.
- the term “essentially free” means that the conversion compositions and/or coatings or layers, respectively, formed from the same contain less than 1 ppm of any or all of the elements or compounds listed in the preceding paragraph, if any at all.
- the term “completely free” means that the conversion compositions and/or coatings or layers, respectively, formed from the same contain less than 1 ppb of any or all of the elements or compounds listed in the preceding paragraph, if any at all.
- the conversion composition may, in some instances, exclude phosphate ions or phosphate-containing compounds and/or the formation of sludge, such as aluminum phosphate, iron phosphate, and/or zinc phosphate, formed in the case of using a treating agent based on zinc phosphate.
- phosphate-containing compounds include compounds containing the element phosphorous such as ortho phosphate, pyrophosphate, metaphosphate, tripolyphosphate, organophosphonates, and the like, and can include, but are not limited to, monovalent, divalent, or trivalent cations such as: sodium, potassium, calcium, zinc, nickel, manganese, aluminum and/or iron.
- a composition and/or a layer or coating comprising the same is substantially free, essentially free, or completely free of phosphate, this includes phosphate ions or compounds containing phosphate in any form.
- conversion composition and/or layers deposited from the same may be substantially free, or in some cases may be essentially free, or in some cases may be completely free, of one or more of any of the ions or compounds listed in the preceding paragraph.
- a conversion composition and/or layers deposited from the same that is substantially free of phosphate means that phosphate ions or compounds containing phosphate are not intentionally added, but may be present in trace amounts, such as because of impurities or unavoidable contamination from the environment. In other words, the amount of material is so small that it does not affect the properties of the composition; this may further include that phosphate is not present in the conversion compositions and/or layers deposited from the same in such a level that they cause a burden on the environment.
- substantially free means that the conversion compositions and/or layers deposited from the same contain less than 5 ppm of any or all of the phosphate anions or compounds listed in the preceding paragraph, based on total weight of the composition or the layer, respectively, if any at all.
- essentially free means that the conversion compositions and/or layers comprising the same contain less than 1 ppm of any or all of the phosphate anions or compounds listed in the preceding paragraph.
- completely free means that the conversion compositions and/or layers comprising the same contain less than 1 ppb of any or all of the phosphate anions or compounds listed in the preceding paragraph, if any at all.
- the pH of the conversion composition may be 1.0 to 4.5, such as 3 to 4, and may be adjusted using, for example, any acid and/or base as is necessary.
- the pH of the conversion composition may be maintained through the inclusion of an acidic material, including water soluble and/or water dispersible acids, such as nitric acid, sulfuric acid, and/or phosphoric acid.
- the pH of the composition may be maintained through the inclusion of a basic material, including water soluble and/or water dispersible bases, such as sodium hydroxide, sodium carbonate, potassium hydroxide, ammonium hydroxide, ammonia, and/or amines such as triethylamine, methylethyl amine, or mixtures thereof.
- a basic material including water soluble and/or water dispersible bases, such as sodium hydroxide, sodium carbonate, potassium hydroxide, ammonium hydroxide, ammonia, and/or amines such as triethylamine, methylethyl amine, or mixtures thereof.
- the conversion composition may comprise an aqueous medium and may optionally contain other materials such as nonionic surfactants and auxiliaries conventionally used in the art of conversion compositions.
- water dispersible organic solvents for example, alcohols with up to about 8 carbon atoms such as methanol, isopropanol, and the like, may be present; or glycol ethers such as the monoalkyl ethers of ethylene glycol, diethylene glycol, or propylene glycol, and the like.
- water dispersible organic solvents are typically used in amounts up to about ten percent by volume, based on the total volume of aqueous medium.
- surfactants that function as defoamers or substrate wetting agents.
- Anionic, cationic, amphoteric, and/or nonionic surfactants may be used.
- Defoaming surfactants may optionally be present at levels up to 1 weight percent, such as up to 0.1 percent by weight, and wetting agents are typically present at levels up to 2 percent, such as up to 0.5 percent by weight, based on the total weight of the conversion composition.
- the conversion composition and/or films deposited or formed therefrom may further comprise silicon in amounts of at least 10 ppm, based on total weight of the conversion composition, such as at least 20 ppm, such as at least 50 ppm.
- the conversion composition and/or films deposited or formed therefrom may comprise silicon in amounts of less than 500 ppm, based on total weight of the conversion composition, such as less than 250 ppm, such as less than 100 ppm.
- the conversion composition and/or films deposited or formed therefrom may comprise silicon in amounts of 10 ppm to 500 ppm, based on total weight of the conversion composition, such as 20 ppm to 250 ppm, such as 50 ppm to 100 ppm.
- the conversion composition of the present invention and/or films deposited or formed therefrom may be substantially free, or, in some cases, completely free of silicon.
- the conversion composition may comprise a carrier, often an aqueous medium, so that the composition is in the form of a solution or dispersion of the lanthanide and/or Group IIIB metal in the carrier.
- the solution or dispersion may be brought into contact with the substrate by any of a variety of known techniques, such as dipping or immersion, spraying, intermittent spraying, dipping followed by spraying, spraying followed by dipping, brushing, or roll-coating.
- the solution or dispersion when applied to the metal substrate is at a temperature ranging from 40° F. to 160° F., such as 60° F. to 110° F., such as 70° F. to 90° F.
- the conversion process may be carried out at ambient or room temperature.
- the contact time is often from 30 seconds to 15 minutes, such as 4 minutes to 10 minutes.
- the substrate optionally may be air dried at room temperature or may be dried with hot air, for example, by using an air knife, by flashing off the water by brief exposure of the substrate to a high temperature, such as by drying the substrate in an oven at 15° C. to 100° C., such as 20° C. to 90° C., or in a heater assembly using, for example, infrared heat, such as for 10 minutes at 70° C., or by passing the substrate between squeegee rolls.
- a high temperature such as by drying the substrate in an oven at 15° C. to 100° C., such as 20° C. to 90° C., or in a heater assembly using, for example, infrared heat, such as for 10 minutes at 70° C., or by passing the substrate between squeegee rolls.
- the substrate optionally may be rinsed with tap water, deionized water, and/or an aqueous solution of rinsing agents in order to remove any residue and then optionally may be dried, for example air dried or dried with hot air as described in the preceding sentence.
- the substrate having been contacted with the conversion composition and having the layer formed from the sealing composition has at least a 50% reduction in the number of pits on the substrate surface compared to a substrate having the film formed from the conversion composition or the layer formed from the sealing composition but not the film and the seal following 3 day exposure in neutral salt spray cabinet operated according to ASTM B117.
- the substrate having the film formed from the conversion composition and the layer formed from the sealing composition has at least a 50% reduction in the number of pits on the substrate surface compared to a substrate having the film formed from the conversion composition or the layer formed from the sealing composition but not the film and the seal following 3 day exposure in neutral salt spray cabinet operated according to ASTM BI 17.
- a substrate comprising, or in some instances consisting essentially of, or in some instances consisting of, a layer having a thickness of 25 nm to 250 nm formed from a sealing composition comprising, or in some instances consisting essentially of, or in some instances, consisting of, a lithium source.
- the substrate may comprise an aluminum alloy comprising copper in an amount of 1 percent by weight to 10 percent by weight.
- the substrate may comprise an aluminum alloy comprising copper in an amount of 1 percent by weight to 10 percent by weight.
- a method of treating a substrate comprising, or in some instances consisting essentially of, or in some instances consisting of, (a) contacting at least a portion of the substrate surface with a conversion composition comprising, or in some instances consisting essentially of, or in some instances consisting of, a lanthanide, a Group IIIB metal, a Group IVB metal, or combinations thereof; and (b) contacting at least a portion of the substrate surface contacted with the conversion composition with a sealing composition comprising, or in some instances consisting essentially of, or in some instances consisting of, a lithium source.
- a coating composition comprising a film-forming resin may be deposited onto at least a portion of the surface of the substrate that has been contacted with the sealing composition.
- Any suitable technique may be used to deposit such a coating composition onto the substrate, including, for example, brushing, dipping, flow coating, spraying and the like.
- depositing of a coating composition may comprise an electrocoating step wherein an electrodepositable composition is deposited onto a metal substrate by electrodeposition.
- such depositing of a coating composition comprises a powder coating step.
- the coating composition may be a liquid coating composition.
- the coating composition may comprise a thermosetting film-forming resin or a thermoplastic film-forming resin.
- film-forming resin refers to resins that can form a self-supporting continuous film on at least a horizontal surface of a substrate upon removal of any diluents or carriers present in the composition or upon curing at ambient or elevated temperature.
- Conventional film-forming resins that may be used include, without limitation, those typically used in automotive OEM coating compositions, automotive refinish coating compositions, industrial coating compositions, architectural coating compositions, coil coating compositions, and aerospace coating compositions, among others.
- thermosetting refers to resins that “set” irreversibly upon curing or crosslinking, wherein the polymer chains of the polymeric components are joined together by covalent bonds. This property is usually associated with a cross-linking reaction of the composition constituents often induced, for example, by heat or radiation. Curing or crosslinking reactions also may be carried out under ambient conditions. Once cured or crosslinked, a thermosetting resin will not melt upon the application of heat and is insoluble in solvents.
- thermoplastic refers to resins that comprise polymeric components that are not joined by covalent bonds and thereby can undergo liquid flow upon heating and are soluble in solvents.
- an electrodepositable coating composition comprising a water-dispersible, ionic salt group-containing film-forming resin that may be deposited onto the substrate by an electrocoating step wherein the electrodepositable coating composition is deposited onto the metal substrate by electrodeposition.
- the ionic salt group-containing film-forming polymer may comprise a cationic salt group containing film-forming polymer for use in a cationic electrodepositable coating composition.
- the term “cationic salt group-containing film-forming polymer” refers to polymers that include at least partially neutralized cationic groups, such as sulfonium groups and ammonium groups, that impart a positive charge.
- the cationic salt group-containing film-forming polymer may comprise active hydrogen functional groups, including, for example, hydroxyl groups, primary or secondary amine groups, and thiol groups. Cationic salt group-containing film-forming polymers that comprise active hydrogen functional groups may be referred to as active hydrogen-containing, cationic salt group-containing film-forming polymers.
- polymers that are suitable for use as the cationic salt group-containing film-forming polymer include, but are not limited to, alkyd polymers, acrylics, polyepoxides, polyamides, polyurethanes, polyureas, polyethers, and polyesters, among others.
- the cationic salt group-containing film-forming polymer may be present in the cationic electrodepositable coating composition in an amount of 40% to 90% by weight, such as 50% to 80% by weight, such as 60% to 75% by weight, based on the total weight of the resin solids of the electrodepositable coating composition.
- the “resin solids” include the ionic salt group-containing film-forming polymer, curing agent, and any additional water-dispersible non-pigmented component(s) present in the electrodepositable coating composition.
- the ionic salt group containing film-forming polymer may comprise an anionic salt group containing film-forming polymer for use in an anionic electrodepositable coating composition.
- anionic salt group containing film-forming polymer refers to an anionic polymer comprising at least partially neutralized anionic functional groups, such as carboxylic acid and phosphoric acid groups that impart a negative charge.
- the anionic salt group-containing film-forming polymer may comprise active hydrogen functional groups.
- Anionic salt group-containing film-forming polymers that comprise active hydrogen functional groups may be referred to as active hydrogen-containing, anionic salt group-containing film-forming polymers.
- the anionic salt group-containing film-forming polymer may comprise base-solubilized, carboxylic acid group-containing film-forming polymers such as the reaction product or adduct of a drying oil or semi-drying fatty acid ester with a dicarboxylic acid or anhydride; and the reaction product of a fatty acid ester, unsaturated acid or anhydride and any additional unsaturated modifying materials which are further reacted with polyol. Also suitable are the at least partially neutralized interpolymers of hydroxy-alkyl esters of unsaturated carboxylic acids, unsaturated carboxylic acid and at least one other ethylenically unsaturated monomer.
- Still another suitable anionic electrodepositable resin comprises an alkyd-aminoplast vehicle, i.e., a vehicle containing an alkyd resin and an amine-aldehyde resin.
- Another suitable anionic electrodepositable resin composition comprises mixed esters of a resinous polyol.
- Other acid functional polymers may also be used such as phosphatized polyepoxide or phosphatized acrylic polymers. Exemplary phosphatized polyepoxides are disclosed in U.S. Patent Application Publication No. 2009-0045071 at [0004]-[0015] and U.S. patent application Ser. No. 13/232,093 at [0014]-[0040], the cited portions of which being incorporated herein by reference.
- the anionic salt group-containing film-forming polymer may be present in the anionic electrodepositable coating composition in an amount 50% to 90%, such as 55% to 80%, such as 60% to 75%, based on the total weight of the resin solids of the electrodepositable coating composition.
- the electrodepositable coating composition may further comprise a curing agent.
- the curing agent may react with the reactive groups, such as active hydrogen groups, of the ionic salt group-containing film-forming polymer to effectuate cure of the coating composition to form a coating.
- suitable curing agents are at least partially blocked polyisocyanates, aminoplast resins and phenoplast resins, such as phenolformaldehyde condensates including allyl ether derivatives thereof.
- the curing agent may be present in the cationic electrodepositable coating composition in an amount of 10% to 60% by weight, such as 20% to 50% by weight, such as 25% to 40% by weight, based on the total weight of the resin solids of the electrodepositable coating composition.
- the curing agent may be present in the anionic electrodepositable coating composition in an amount of 10% to 50% by weight, such as 20% to 45% by weight, such as 25% to 40% by weight, based on the total weight of the resin solids of the electrodepositable coating composition.
- the electrodepositable coating composition may further comprise other optional ingredients, such as a pigment composition and, if desired, various additives such as fillers, plasticizers, anti-oxidants, biocides, UV light absorbers and stabilizers, hindered amine light stabilizers, defoamers, fungicides, dispersing aids, flow control agents, surfactants, wetting agents, or combinations thereof.
- additives such as fillers, plasticizers, anti-oxidants, biocides, UV light absorbers and stabilizers, hindered amine light stabilizers, defoamers, fungicides, dispersing aids, flow control agents, surfactants, wetting agents, or combinations thereof.
- the electrodepositable coating composition may comprise water and/or one or more organic solvent(s).
- Water can for example be present in amounts of 40% to 90% by weight, such as 50% to 75% by weight, based on total weight of the electrodepositable coating composition.
- the organic solvents may typically be present in an amount of less than 10% by weight, such as less than 5% by weight, based on total weight of the electrodepositable coating composition.
- the electrodepositable coating composition may in particular be provided in the form of an aqueous dispersion.
- the total solids content of the electrodepositable coating composition may be from 1% to 50% by weight, such as 5% to 40% by weight, such as 5% to 20% by weight, based on the total weight of the electrodepositable coating composition.
- total solids refers to the non-volatile content of the electrodepositable coating composition, i.e., materials which will not volatilize when heated to 110° C. for 15 minutes.
- the cationic electrodepositable coating composition may be deposited upon an electrically conductive substrate by placing the composition in contact with an electrically conductive cathode and an electrically conductive anode, with the surface to be coated being the cathode.
- the anionic electrodepositable coating composition may be deposited upon an electrically conductive substrate by placing the composition in contact with an electrically conductive cathode and an electrically conductive anode, with the surface to be coated being the anode.
- An adherent film of the electrodepositable coating composition is deposited in a substantially continuous manner on the cathode or anode, respectively, when a sufficient voltage is impressed between the electrodes.
- the applied voltage may be varied and can be, for example, as low as one volt to as high as several thousand volts, such as between 50 and 500 volts.
- Current density is usually between 1.0 ampere and 15 amperes per square foot (10.8 to 161.5 amperes per square meter) and tends to decrease quickly during the electrodeposition process, indicating formation of a continuous self-insulating film.
- the coated substrate is heated to a temperature and for a time sufficient to cure the electrodeposited coating on the substrate.
- the coated substrate may be heated to a temperature ranging from 250° F. to 450° F. (121.1° C. to 232.2° C.), such as from 275° F. to 400° F. (135° C. to 204.4° C.), such as from 300° F. to 360° F. (149° C. to 180° C.).
- the coated substrate may be heated to a temperature ranging from 200° F. to 450° F. (93° C. to 232.2° C.), such as from 275° F.
- the curing time may be dependent upon the curing temperature as well as other variables, for example, the film thickness of the electrodeposited coating, level and type of catalyst present in the composition and the like.
- the curing time can range from 10 minutes to 60 minutes, such as 20 to 40 minutes.
- the thickness of the resultant cured electrodeposited coating may range from 2 to 50 microns.
- a powder coating composition may then be deposited onto at least a portion of the surface of the substrate.
- powder coating composition refers to a coating composition which is completely free of water and/or solvent. Accordingly, the powder coating composition disclosed herein is not synonymous to waterborne and/or solvent-borne coating compositions known in the art.
- the powder coating composition may comprise (a) a film forming polymer having a reactive functional group; and (b) a curing agent that is reactive with the functional group.
- powder coating compositions that may be used in the present invention include the polyester-based ENVIROCRON line of powder coating compositions (commercially available from PPG Industries, Inc.) or epoxy-polyester hybrid powder coating compositions.
- curable powder coating compositions generally comprising (a) at least one tertiary aminourea compound, at least one tertiary aminourethane compound, or mixtures thereof, and (b) at least one film-forming epoxy-containing resin and/or at least one siloxane-containing resin (such as those described in U.S. Pat. No. 7,432,333, assigned to PPG Industries, Inc. and incorporated herein by reference); and those comprising a solid particulate mixture of a reactive group-containing polymer having a T g of at least 30° C. (such as those described in U.S. Pat. No. 6,797,387, assigned to PPG Industries, Inc. and incorporated herein by reference).
- the coating is often heated to cure the deposited composition.
- the heating or curing operation is often carried out at a temperature in the range of from 150° C. to 200° C., such as from 170° C. to 190° C., for a period of time ranging from 10 to 20 minutes.
- the thickness of the resultant film is from 50 microns to 125 microns.
- the coating composition may be a liquid coating composition.
- liquid coating composition refers to a coating composition which contains a portion of water and/or solvent. Accordingly, the liquid coating composition disclosed herein is synonymous to waterborne and/or solventborne coating compositions known in the art.
- the liquid coating composition may comprise, for example, (a) a film forming polymer having a reactive functional group; and (b) a curing agent that is reactive with the functional group.
- the liquid coating may contain a film forming polymer that may react with oxygen in the air or coalesce into a film with the evaporation of water and/or solvents. These film forming mechanisms may require or be accelerated by the application of heat or some type of radiation such as Ultraviolet or Infrared.
- liquid coating compositions examples include the SPECTRACRON® line of solventbased coating compositions, the AQUACRON® line of waterbased coating compositions, and the RAYCRON® line of UV cured coatings (all commercially available from PPG Industries, Inc.).
- Suitable film forming polymers that may be used in the liquid coating composition of the present invention may comprise a (poly)ester, an alkyd, a (poly)urethane, an isocyanurate, a (poly)urea, a (poly)epoxy, an anhydride, an acrylic, a (poly)ether, a (poly)sulfide, a (poly)amine, a (poly)amide, (poly)vinyl chloride, (poly)olefin, (poly)vinylidene fluoride, (poly)siloxane, or combinations thereof.
- the substrate that has been contacted with the sealing composition may also be contacted with a primer composition and/or a topcoat composition.
- the primer coat may be, for examples, chromate-based primers and advanced performance topcoats.
- the primer coat can be a conventional chromate based primer coat, such as those available from PPG Industries, Inc. (product code 44GN072), or a chrome-free primer such as those available from PPG (DESOPRIME CA7502, DESOPRIME CA7521, Deft 02GN083, Deft 02GN084).
- the primer coat can be a chromate-free primer coat, such as the coating compositions described in U.S. patent application Ser. No.
- the substrate of the present invention also may comprise a topcoat.
- topcoat refers to a mixture of binder(s) which can be an organic or inorganic based polymer or a blend of polymers, typically at least one pigment, can optionally contain at least one solvent or mixture of solvents, and can optionally contain at least one curing agent.
- a topcoat is typically the coating layer in a single or multi-layer coating system whose outer surface is exposed to the atmosphere or environment, and its inner surface is in contact with another coating layer or polymeric substrate. Examples of suitable topcoats include those conforming to MIL-PRF-85285D, such as those available from PPG (Deft 03W127A and Deft 03GY292).
- the topcoat may be an advanced performance topcoat, such as those available from PPG (Defthane® ELTTM 99GY001 and 99W009).
- PPG Dethane® ELTTM 99GY001 and 99W009
- other topcoats and advanced performance topcoats can be used in the present invention as will be understood by those of skill in the art with reference to this disclosure.
- the metal substrate also may comprise a self-priming topcoat, or an enhanced self-priming topcoat.
- self-priming topcoat also referred to as a “direct to substrate” or “direct to metal” coating, refers to a mixture of a binder(s), which can be an organic or inorganic based polymer or blend of polymers, typically at least one pigment, can optionally contain at least one solvent or mixture of solvents, and can optionally contain at least one curing agent.
- enhanced self-priming topcoat also referred to as an “enhanced direct to substrate coating” refers to a mixture of functionalized fluorinated binders, such as a fluoroethylene-alkyl vinyl ether in whole or in part with other binder(s), which can be an organic or inorganic based polymer or blend of polymers, typically at least one pigment, can optionally contain at least one solvent or mixture of solvents, and can optionally contain at least one curing agent.
- binder(s) typically at least one pigment
- self-priming topcoats include those that conform to TT-P-2756A.
- self-priming topcoats examples include those available from PPG (03W169 and 03GY369), and examples of enhanced self-priming topcoats include Defthane® ELTTM/ESPT and product code number 97GY121, available from PPG.
- other self-priming topcoats and enhanced self-priming topcoats can be used in the coating system according to the present invention as will be understood by those of skill in the art with reference to this disclosure.
- the self-priming topcoat and enhanced self-priming topcoat may be applied directly to the sealed substrate.
- the self-priming topcoat and enhanced self-priming topcoat can optionally be applied to an organic or inorganic polymeric coating, such as a primer or paint film.
- the self-priming topcoat layer and enhanced self-priming topcoat is typically the coating layer in a single or multi-layer coating system where the outer surface of the coating is exposed to the atmosphere or environment, and the inner surface of the coating is typically in contact with the substrate or optional polymer coating or primer.
- the topcoat, self-priming topcoat, and enhanced self-priming topcoat can be applied to the sealed substrate, in either a wet or “not fully cured” condition that dries or cures over time, that is, solvent evaporates and/or there is a chemical reaction.
- the coatings can dry or cure either naturally or by accelerated means for example, an ultraviolet light cured system to form a film or “cured” paint.
- the coatings can also be applied in a semi or fully cured state, such as an adhesive.
- a colorant and, if desired, various additives such as surfactants, wetting agents or catalyst can be included in the coating composition (electrodepositable, powder, or liquid).
- the term “colorant” means any substance that imparts color and/or other opacity and/or other visual effect to the composition.
- Example colorants include pigments, dyes and tints, such as those used in the paint industry and/or listed in the Dry Color Manufacturers Association (DCMA), as well as special effect compositions.
- the colorant can be present in the coating composition in any amount sufficient to impart the desired visual and/or color effect.
- the colorant may comprise from 1 to 65 weight percent, such as from 3 to 40 weight percent or 5 to 35 weight percent, with weight percent based on the total weight of the composition.
- each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
- a closed or open-ended numerical range is described herein, all numbers, values, amounts, percentages, subranges and fractions within or encompassed by the numerical range are to be considered as being specifically included in and belonging to the original disclosure of this application as if these numbers, values, amounts, percentages, subranges and fractions had been explicitly written out in their entirety.
- the term “substantially free,” when used with respect to the absence of a particular material, means that such material, if present at all in a composition, a bath containing the composition, and/or layers formed from and comprising the composition, only is present in a trace amount of 5 ppm or less based on a total weight of the composition or layer(s), as the case may be, excluding any amount of such material that may be present or derived as a result of drag-in, substrate(s), and/or dissolution of equipment).
- the term “essentially free,” when used with respect to the absence of a particular material, means that such material, if present at all in a composition, a bath containing the composition, and/or layers formed from and comprising the composition, only is present in a trace amount of 1 ppm or less based on a total weight of the composition or layer(s), as the case may be.
- the term “completely free,” when used with respect to the absence of a particular material, means that such material, if present at all in a composition, a bath containing the composition, and/or layers formed from and comprising the composition, is absent from the composition, the bath containing the composition, and/or layers formed from and comprising same (i.e., the composition, bath containing the composition, and/or layers formed from and comprising the composition contain 0 ppm of such material).
- the terms “on,” “onto,” “applied on,” “applied onto,” “formed on,” “deposited on,” “deposited onto,” mean formed, overlaid, deposited, and/or provided on but not necessarily in contact with the surface.
- a coating layer “formed over” a substrate does not preclude the presence of one or more other intervening coating layers of the same or different composition located between the formed coating layer and the substrate.
- salt refers to an ionic compound made up of metal cations and non-metallic anions and having an overall electrical charge of zero. Salts may be hydrated or anhydrous.
- aqueous composition refers to solution or dispersion in a medium that comprises predominantly water.
- the aqueous medium may comprise water in an amount of more than 50 wt. %, or more than 70 wt. % or more than 80 wt. % or more than 90 wt. % or more than 95 wt. %, based on the total weight of the medium.
- the aqueous medium may for example consist substantially of water.
- conversion composition refers to a composition that is capable of reacting with and chemically altering the substrate surface and binding to it to form a film that affords corrosion protection.
- conversion bath refers to an aqueous bath containing the conversion composition and that may contain components that are byproducts of the process of contacting a substrate with the conversion composition.
- conversion composition metal cation(s) refers to metal cations of a lanthanide series element, a Group IIA metal, a Group IIIB metal, a Group IVB metal, a Group VB metal, a Group VIB metal, a Group VIIB metal, and/or a Group XII metal.
- a “sealing composition” refers to a composition, e.g. a solution or dispersion, that affects a substrate surface or a material deposited onto a substrate surface in such a way as to alter the physical and/or chemical properties of the substrate surface (i.e., the composition affords corrosion protection).
- Group IA metal refers to an element that is in Group IA of the CAS version of the Periodic Table of the Elements as is shown, for example, in the Handbook of Chemistry and Physics, 63 rd edition (1983), corresponding to Group 1 in the actual IUPAC numbering.
- Group IA metal compound refers to compounds that include at least one element that is in Group IA of the CAS version of the Periodic Table of the Elements.
- Group IIIB metal refers to yttrium and scandium of the CAS version of the Periodic Table of the Elements as is shown, for example, in the Handbook of Chemistry and Physics, 63 rd edition (1983), corresponding to Group 3 in the actual IUPAC numbering. For clarity, “Group IIIB metal” expressly excludes lanthanide series elements.
- Group IIIB metal compound refers to compounds that include at least one element that is in group IIIB of the CAS version of the Periodic Table of the Elements as defined above.
- Group IVB metal refers to an element that is in group IVB of the CAS version of the Periodic Table of the Elements as is shown, for example, in the Handbook of Chemistry and Physics, 63 rd edition (1983), corresponding to Group 4 in the actual IUPAC numbering.
- Group IVB metal compound refers to compounds that include at least one element that is in Group IVB of the CAS version of the Periodic Table of the Elements.
- Group VB metal refers to an element that is in group VB of the CAS version of the Periodic Table of the Elements as is shown, for example, in the Handbook of Chemistry and Physics, 63 rd edition (1983), corresponding to Group 5 in the actual IUPAC numbering.
- Group VB metal compound refers to compounds that include at least one element that is in Group VB of the CAS version of the Periodic Table of the Elements.
- Group VIB metal refers to an element that is in group VIB of the CAS version of the Periodic Table of the Elements as is shown, for example, in the Handbook of Chemistry and Physics, 63 rd edition (1983), corresponding to Group 6 in the actual IUPAC numbering.
- Group VIB metal compound refers to compounds that include at least one element that is in Group VIB of the CAS version of the Periodic Table of the Elements.
- the term “lanthanide series elements” refers to elements 57-71 of the CAS version of the Periodic Table of the Elements and includes elemental versions of the lanthanide series elements.
- the lanthanide series elements may be those which have both common oxidation states of +3 and +4, referred to hereinafter as +3/+4 oxidation states.
- lanthanide compound refers to compounds that include at least one of elements 57-71 of the CAS version of the Periodic Table of the Elements.
- halogen refers to any of the elements fluorine, chlorine, bromine, iodine, and astatine of the CAS version of the Periodic Table of the Elements, corresponding to Group VIIA of the periodic table.
- halide refers to compounds that include at least one halogen.
- aluminum when used in reference to a substrate, refers to substrates made of or comprising aluminum and/or aluminum alloy, and clad aluminum substrates.
- the term “oxidizing agent,” when used with respect to a component of the conversion composition, refers to a chemical which is capable of oxidizing at least one of: a metal present in the substrate which is contacted by the conversion composition, a lanthanide series element present in the conversion composition, and/or a metal-complexing agent present in the conversion composition.
- oxidizing agent the phrase “capable of oxidizing” means capable of removing electrons from an atom or a molecule present in the substrate or the conversion composition, as the case may be, thereby decreasing the number of electrons of such atom or molecule.
- Pitting corrosion is the localized formation of corrosion by which cavities or holes are produced in a substrate.
- the term “pit,” as used herein, refers to such cavities or holes resulting from pitting corrosion and is characterized by (1) a rounded, elongated or irregular appearance when viewed normal to the test panel surface, (2) a “comet-tail”, a line, or a “halo” (i.e., a surface discoloration) emanating from the pitting cavity, and (3) the presence of corrosion byproduct (e.g., white, grayish or black granular, powdery or amorphous material) inside or immediately around the pit.
- An observed surface cavity or hole must exhibit at least two of the above characteristics to be considered a corrosion pit. Surface cavities or holes that exhibit only one of these characteristics may require additional analysis before being classified as a corrosion pit. Visual inspection using a microscope with 10 ⁇ magnification is used to determine the presence of corrosion byproducts when corrosion byproducts are not visible with the unaided eye.
- total composition weight refers to the total weight of all ingredients being present in the respective composition including any carriers and solvents.
- a method of treating a substrate comprising: contacting at least a portion of the substrate surface with a sealing composition comprising a lithium cation.
- sealing composition further comprises a carbonate source, a hydroxide source, or combinations thereof.
- the sealing composition further comprises a source of a Group IA metal other than lithium, a Group VB metal source, a Group VIB metal source, a corrosion inhibitor, an indicator compound, or combinations thereof.
- sealing composition is substantially free of fluoride, a Group IIA metal cation, a cobalt ion, a vanadium ion, or combinations thereof.
- any of Aspects 13 or 14, wherein the lanthanide series element cation, Group IIIB metal cation, and/or Group IVB metal cation comprises cerium, praseodymium, yttrium, zirconium, titanium, or combinations thereof.
- the substrate comprises aluminum, aluminum alloys, or combinations thereof.
- the substrate comprises an aluminum alloy comprising copper in an amount of 1 percent by weight to 10 percent by weight.
- a system for treated a substrate comprising;
- a conversion composition for treating at least a portion of the substrate comprising a lanthanide series cation, a Group IIIB metal cation, a Group IVB metal cation, or combinations thereof;
- a sealing composition for treating at least a portion of the substrate, comprising a lithium cation comprising
- a substrate obtainable by the method of any of Aspects 1 to 25.
- a substrate obtainable by the system of any of Aspects 26 to 28.
- substrate treated with the sealing composition has at least a 50% reduction in the number of pits on the substrate surface compared to a substrate not treated with the sealing composition following 3 day exposure in neutral salt spray cabinet operated according to ASTM B117.
- Alfa Aesar (Ward Hill, MA) sodium hydroxide pellets, 98% Alfa Aesar sodium phosphate dodecahydrate, 97% Alfa Aesar polyvinylpyrrolidone (PVP), 8000 m.w.
- Alfa Aesar Allantoin 3 98% Alfa Aesar 2,5-dimercapto-1,3,4-thiadiazole, 98% Acros Organics (Geel, Belgium) Carbowet GA100 4 , 100% Air Products (Cleveland, OH) lithium carbonate, 98% Alfa Aesar sodium vanadium oxide, 96% Ward Hill sodium molybdenum oxide dehydrate, Alfa Aesar 98% 1 A non-silicated cleaner. 2 A deoxidizer. 3 (2,5-dioxo-4-imidazolidinyl) urea. 4 A non-ionic surfactant. *As per the supplier's analytical report, the concentration of cerium in the cerium chloride solution is measured as cerium oxide (CeO 2 ).
- Example B The solution of Example B was prepared using the ingredients shown in Table 5B, per manufacturer's instructions.
- Example C Deoxidizer solutions of Example C was prepared using the ingredients shown in Table 6, per manufacturers' instructions.
- the cerium nitrate, yttrium nitrate and cerium chloride solutions were weighted into individual cups. Then using 500 grams of deionized water, the solutions were transferred to a vessel containing 1000 grams of deionized water under mild agitation. The remaining 453 grams of water was added and the solution was stirred for 10 minutes to ensure uniformity before the hydrogen peroxide was added. The final solution stirred for a minimum of 30 minutes before use.
- Example F For the conversion coating composition of Example F, solutions were prepared by adding the cerium chloride solution to the full amount of deionized water under mild agitation. The solution was stirred for 10 minutes to ensure uniformity before the hydrogen peroxide was added. The final solution stirred for a minimum of 30 minutes before use.
- Example G Example H Example I lithium carbonate, grams 3.07 3.07 3.07 deionized water, grams 1996.93 1996.93 1996.93 sodium vanadium oxide, grams — 1.67 — sodium molybdenum oxide — — 1.67 dehydrate, grams
- Example G The sealing solution of Example G was prepared using the ingredients shown in Table 8 by dissolving lithium carbonate in deionized water under mild agitation using the stir plate as described above.
- Example H The sealing solution of Example H was prepared using the ingredients shown in Table 8 by dissolving lithium carbonate in deionized water under mild agitation using the stir plate as described above. Next, the sodium vanadium oxide was added and dissolved under mild agitation as described above.
- Example I The sealing solution of Example I was prepared using the ingredients shown in Table 8 by dissolving lithium carbonate in deionized water under mild agitation using the stir plate as described above. Next, the sodium molybdenum oxide dehydrate was added and dissolved under mild agitation as described above.
- Aluminum 2024T3 bare substrate (Priority Metals, Orange County, Calif.) measuring 3′′ ⁇ 5′′ ⁇ 0.032′′ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning.
- the panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation.
- the panel was then immersed in two subsequent deionized water rinses for two minutes each, both at ambient temperature with intermittent agitation.
- the panel received a cascading deionized water rinse for 10 seconds.
- the panel was then immersed in the conversion coating composition of Example E for 5 minutes at ambient temperature and without agitation.
- the panel received an immersion rinse in deionized water for 1 minute at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse.
- the panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3′′ ⁇ 5′′ ⁇ 0.032′′ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning.
- the panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation.
- the panel was then immersed in two subsequent deionized water rinses for two minutes each, both at ambient temperature with intermittent agitation.
- the panel received a cascading deionized water rinse for 10 seconds.
- the panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation.
- the panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3′′ ⁇ 5′′ ⁇ 0.032′′ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning.
- the panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation.
- the panel was then immersed in two subsequent deionized water rinses for two minutes each, both at ambient temperature with intermittent agitation.
- the panel received a cascading deionized water rinse for 10 seconds.
- the panel was then immersed in the conversion coating composition of Example E for 5 minutes at ambient temperature and without agitation.
- the panel After the conversion coating, the panel received an immersion rinse in deionized water for 1 minute at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse. The panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation. The panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3′′ ⁇ 5′′ ⁇ 0.032′′ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning.
- the panel was immersed in the cleaner solution of Example B for 2 minutes at 55° C. with mild agitation.
- the panel was then immersed in a tap water rinse for one minute at ambient temperature with mild agitation followed by a 10 second cascading tap water rinse.
- the panel was immersed in a deoxidizing solution of Example C for 1.5 minutes at ambient temperature followed by a one minute immersion rinse in tap water at ambient temperature and mild agitation followed by a 10 second cascading rinse.
- the panel was then immersed in the conversion coating composition of Example E for 5 minutes at ambient temperature and without agitation.
- the panel After the conversion coating, the panel received an immersion rinse in deionized water for 1 minute at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse. The panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation. The panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3′′ ⁇ 5′′ ⁇ 0.032′′ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning.
- the panel was immersed in the cleaner solution of Example B for 2 minutes at 55° C. with mild agitation.
- the panel was then immersed in a tap water rinse for one minute at ambient temperature with mild agitation followed by a 10 second cascading tap water rinse.
- the panel was immersed in a deoxidizing solution of Example C for 1.5 minutes at ambient temperature followed by a one minute immersion rinse in tap water at ambient temperature and mild agitation followed by a 10 second cascading rinse.
- the panel was then immersed in the conversion coating composition of Example F for 7 minutes at ambient temperature and without agitation.
- the panel After the conversion coating, the panel received an immersion rinse in deionized water for 1 minute at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse. The panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation. The panel was air dried at ambient conditions overnight before testing.
- a 3′ ⁇ 10′′ ⁇ 0.032′′ panel of Al 2024-T3 was solvent wiped on both sides with Methyl Ethyl Ketone using a lint-free paper towel until the surface was visually free from grease and oil.
- the panel was then immersed in the cleaner solution of Example A for 7 minutes at ambient temperature.
- the panel was then rinsed using a de-ionized water spray rinse for two minutes followed by a de-ionized water immersion rinse for two minutes.
- the panel was then immersed in the conversion coating composition of Example E for 5 minutes at ambient temperature.
- the panel was then immersed in de-ionized water for two minutes, followed by a second de-ionized water rinse for two minutes.
- the metal substrate was then immersed in the sealing composition of Example G for two minutes.
- the panel was allowed to air dry at ambient conditions prior to testing.
- a 3′′ ⁇ 10′′ ⁇ 0.032′′ panel of Al 2024-T3 was solvent wiped on both sides with Methyl Ethyl Ketone using a lint-free paper towel until the surface was visually free from grease and oil.
- the panel was then immersed in the cleaner solution of Example A for 7 minutes at ambient temperature.
- the panel was then rinsed using a de-ionized water spray rinse for two minutes followed by a de-ionized water immersion rinse for two minutes.
- the panel was then immersed in the conversion coating composition of Example E for 5 minutes at ambient temperature.
- the panel was then immersed in de-ionized water for two minutes, followed by a second de-ionized water rinse for two minutes.
- the metal substrate was then immersed in the sealing composition of Example H for 2 minutes.
- the panel was allowed to air dry at ambient conditions prior to testing.
- a 3′′ ⁇ 10′′ ⁇ 0.032′′ panel of Al 2024-T3 was solvent wiped on both sides with Methyl Ethyl Ketone using a lint-free paper towel until the surface was visually free from grease and oil.
- the panel was then immersed in the cleaner solution of Example A for 7 minutes.
- the panel was rinsed using a de-ionized water spray rinse for two minutes followed by a de-ionized water immersion rinse for two minutes.
- the panel was then immersed in the conversion coating composition of Example E for 5 minutes at ambient temperature.
- the panel was then immersed in de-ionized water for two minutes, followed by a second de-ionized water rinse for two minutes.
- the metal substrate was then immersed in the sealing composition of Example I described above for 2 minutes.
- the panel was allowed to air dry at ambient conditions prior to testing.
- Examples 1-5 were evaluated for corrosion resistance by placing each panel in a 7 day exposure neutral salt spray cabinet operated according to ASTM B117. Corrosion performance was evaluated by counting the number of pits visible to the naked eye on the panels. Data are reported in Table 9.
- Example E None 100+ pits 662 (Ce) 2 Example A None Example G 100+ pits 299 (Ce) - baseline 3 Example A Example E Example G 0 pits 768 (Ce) 4 Example B/C Example E Example G 100+ pits 313 (Ce) 5 Example B/C Example F Example G 3 pits 1478 (Ce) 3 days 6 Example A Example E Example G 8 (rating) n/a 7 Example A Example E Example H 9 (rating) n/a 8 Example A Example E Example I 10 (rating) n/a
- Table 9 demonstrate that the combination contacting a substrate surface with a lanthanide-containing conversion composition and a lithium-containing sealing composition that includes either a molybdenum salt or a vanadium salt further reduced the level of pitting on the substrate surface following 3 day exposure in neutral salt spray cabinet operated according to ASTM B117 compared to a substrate surface that has been contacted with the conversion composition and a sealing composition that does not include the molybdenum salt or the vanadium salt.
- Table 9 demonstrate that the combination of a film formed from a lanthanide-containing conversion composition with a layer formed from a lithium-containing sealing composition results in at least a 50% reduction in the number of pits on the substrate surface compared to a substrate surface that has the conversion composition film or the sealing composition layer but not both following 7 day exposure in neutral salt spray cabinet operated according to ASTM B117.
- the cerium nitrate and cerium chloride solutions were weighted into individual cups. Then using 500 grams of deionized water, the solutions were transferred to a vessel containing 1000 grams of deionized water under mild agitation. The remaining 374.88 grams of water were added and the solution was stirred for 10 minutes to ensure uniformity before the hydrogen peroxide was added. The final solution stirred for a minimum of 30 minutes before use.
- the yttrium nitrate and yttrium chloride solutions were weighted into individual cups. Then using 500 grams of deionized water, the solutions were transferred to a vessel containing 1000 grams of deionized water under mild agitation. The remaining 380.03 grams of water were added and the solution was stirred for 10 minutes to ensure uniformity before the hydrogen peroxide was added. The final solution stirred for a minimum of 30 minutes before use.
- the entire amount of deionized water was weighed into a container.
- the zirconium salt was measured into a separate cup then transferred into the vessel containing the deionized water while under moderate stirring.
- the solution continued to stir for 15 minutes to allow the entire amount of salt to dissolve. This exact process was used to prepare the titanium solution.
- Aluminum 2024T3 bare substrate (Priority Metals, Orange County, Calif.) measuring 3′′ ⁇ 5′′ ⁇ 0.032′′ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning.
- the panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation.
- the panel was then immersed in two subsequent deionized water rinses for two minutes each, both at ambient temperature with intermittent agitation. After the second rinse, the panel was air dried at ambient conditions overnight before testing.
- the panel was placed in 3 day and 7 day exposure in neutral salt spray cabinet operated according to ASTM B117. Corrosion performance was evaluated by counting the number of pits visible to the naked eye on the panels. Data are reported in Table 14.
- Aluminum 2024T3 bare substrate (Priority Metals, Orange County, Calif.) measuring 3′′ ⁇ 5′′ ⁇ 0.032′′ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning.
- the panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation.
- the panel was then immersed in two subsequent deionized water rinses for two minutes each, both at ambient temperature with intermittent agitation. After the second rinse, the panel received a cascading deionized water rinse for 10 seconds.
- the panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation.
- the panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate (Priority Metals, Orange County, Calif.) measuring 3′′ ⁇ 5′′ ⁇ 0.032′′ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning.
- the panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation.
- the panel was then immersed in two subsequent deionized water rinses for two minutes each, both at ambient temperature with intermittent agitation.
- the panel received a cascading deionized water rinse for 10 seconds.
- the panel was then immersed in the conversion coating of Example J for 5 minutes at ambient temperature and without agitation.
- the panel received an immersion rinse in deionized water for 2 minutes at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse.
- the panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate (Priority Metals, Orange County, Calif.) measuring 3′′ ⁇ 5′′ ⁇ 0.032′′ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning.
- the panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation.
- the panel was then immersed in two subsequent deionized water rinses for two minutes each, both at ambient temperature with intermittent agitation.
- the panel received a cascading deionized water rinse for 10 seconds.
- the panel was then immersed in the conversion coating of Example K for 5 minutes at ambient temperature and without agitation.
- the panel received an immersion rinse in deionized water for 2 minutes at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse.
- the panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3′′ ⁇ 5′′ ⁇ 0.032′′ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning.
- the panel was immersed in the cleaner solution of Example B for 2 minutes at 55° C. with mild agitation.
- the panel was then immersed in a tap water rinse for one minute at ambient temperature with mild agitation followed by a 10 second cascading tap water rinse.
- the panel was immersed in a deoxidizing solution of Example C for 1.5 minutes at ambient temperature followed by a one minute immersion rinse in tap water at ambient temperature and mild agitation followed by a 10 second cascading rinse.
- the panel was then immersed in the conversion coating of Example J for 5 minutes at ambient temperature and without agitation.
- the panel After the conversion coating, the panel received an immersion rinse in deionized water for 2 minutes at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse. The panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation. The panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3′′ ⁇ 5′′ ⁇ 0.032′′ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning.
- the panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation.
- the panel was then immersed in two subsequent deionized water rinses for two minutes each, both at ambient temperature with intermittent agitation.
- the panel received a cascading deionized water rinse for 10 seconds.
- the panel was then immersed in the conversion coating of Example J for 5 minutes at ambient temperature and without agitation.
- the panel After the conversion coating, the panel received an immersion rinse in deionized water for 2 minutes at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse. The panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation. The panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3′′ ⁇ 5′′ ⁇ 0.032′′ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning.
- the panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation.
- the panel was then immersed in two subsequent deionized water rinses for two minutes each, both at ambient temperature with intermittent agitation.
- the panel received a cascading deionized water rinse for 10 seconds.
- the panel was then immersed in the conversion coating of Example K for 5 minutes at ambient temperature and without agitation.
- the panel After the conversion coating, the panel received an immersion rinse in deionized water for 2 minutes at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse. The panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation. The panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3′′ ⁇ 5′′ ⁇ 0.032′′ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning.
- the panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation.
- the panel was then immersed in two subsequent deionized water rinses for two minutes each, both at ambient temperature with intermittent agitation.
- the panel received a cascading deionized water rinse for 10 seconds.
- the panel was then immersed in the conversion coating of Example E for 5 minutes at ambient temperature and without agitation.
- the panel After the conversion coating, the panel received an immersion rinse in deionized water for 2 minutes at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse. The panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation. The panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3′′ ⁇ 5′′ ⁇ 0.032′′ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning.
- the panel was immersed in the cleaner solution of Example B for 2 minutes at 55° C. with mild agitation.
- the panel was then immersed in a tap water rinse for one minute at ambient temperature with mild agitation followed by a 10 second cascading tap water rinse.
- the panel was immersed in a deoxidizing solution of Example C for 1.5 minutes at ambient temperature followed by a one minute immersion rinse in tap water at ambient temperature and mild agitation followed by a 10 second cascading rinse.
- the panel was then immersed in the conversion coating of Example F for 5 minutes at ambient temperature and without agitation.
- the panel After the conversion coating, the panel received an immersion rinse in deionized water for 2 minutes at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse. The panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation. The panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3′′ ⁇ 5′′ ⁇ 0.032′′ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning.
- the panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation.
- the panel was then immersed in an ambient deionized water rinse for 5 seconds followed by an ambient deionized water immersion rinse for 2 minutes with intermittent agitation.
- the panel received a cascading deionized water rinse for 10 seconds.
- the panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation.
- the panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3′′ ⁇ 5′′ ⁇ 0.032′′ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning.
- the panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation.
- the panel was then immersed in an ambient deionized water rinse for 5 seconds followed by an ambient deionized water immersion rinse for 2 minutes with intermittent agitation.
- the panel received a cascading deionized water rinse for 10 seconds.
- the panel was then immersed in the conversion coating of Example L for 1 minute at ambient temperature and without agitation.
- the panel received an immersion rinse in deionized water for 2 minutes at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse.
- the panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3′′ ⁇ 5′′ ⁇ 0.032′′ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning.
- the panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation.
- the panel was then immersed in an ambient deionized water rinse for 5 seconds followed by an ambient deionized water immersion rinse for 2 minutes with intermittent agitation. After the second rinse, the panel received a cascading deionized water rinse for 10 seconds.
- the panel was then immersed in the conversion coating of Example L for 1 minute at ambient temperature and without agitation.
- the panel After the conversion coating, the panel received an immersion rinse in deionized water for 2 minutes at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse. The panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation. The panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3′′ ⁇ 5′′ ⁇ 0.032′′ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning.
- the panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation.
- the panel was then immersed in an ambient deionized water rinse for 5 seconds followed by an ambient deionized water immersion rinse for 2 minutes with intermittent agitation.
- the panel received a cascading deionized water rinse for 10 seconds.
- the panel was then immersed in the conversion coating of Example M for 1 minute at ambient temperature and without agitation.
- the panel received an immersion rinse in deionized water for 2 minutes at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse.
- the panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3′′ ⁇ 5′′ ⁇ 0.032′′ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning.
- the panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation.
- the panel was then immersed in an ambient deionized water rinse for 5 seconds followed by an ambient deionized water immersion rinse for 2 minutes with intermittent agitation. After the second rinse, the panel received a cascading deionized water rinse for 10 seconds.
- the panel was then immersed in the conversion coating of Example M for 1 minute at ambient temperature and without agitation.
- the panel After the conversion coating, the panel received an immersion rinse in deionized water for 2 minutes at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse. The panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation. The panel was air dried at ambient conditions overnight before testing.
- Example AA through MM For each of Examples AA through MM, one panel was placed in a 3 day exposure and one panel was placed in a 7 day exposure in a neutral salt spray cabinet operated according to ASTM B117. Corrosion performance was evaluated by counting the number of pits visible to the naked eye on the panels. Data are reported in Table 14.
- Example AA a metal substrate that was treated with the sealing composition via the method of the present invention provided a reduction in the amount of corrosion on the treated substrate after exposure to neutral salt spray for 7 days.
- Evidence of the reduced corrosion is demonstrated by the occurrence of only 79 pits for Example AA versus 100+ pits for Example AAA.
- Example DD wherein the substrate was first contacted with a conversion coating comprising a lanthanide series element (cerium) and subsequently contacted with a sealing solution comprising a lithium salt, demonstrated a reduced number of corrosion pits after both 3 days and 7 days exposure to neutral salt spray in comparison to both Examples AA (substrate only contacted with the sealing solution) and BB (substrate only contacted with the lanthanide containing conversion coating).
- a conversion coating comprising a lanthanide series element (cerium)
- a sealing solution comprising a lithium salt
- Example EE wherein the substrate was first contacted with a conversion coating comprising a lanthanide series element (cerium) and subsequently contacted with a sealing solution comprising a lithium salt, demonstrated greater than a 50% reduction in the number of corrosion pits after both 3 days and 7 days exposure to neutral salt spray in comparison to both Examples AA (substrate only contacted with the sealing solution) and BB (substrate only contacted with the lanthanide containing conversion coating). Additionally, the number of pits were further reduced relative to Example DD and the detectable level of cerium on the substrate was measurably greater than that measured for Example DD.
- a conversion coating comprising a lanthanide series element (cerium)
- a sealing solution comprising a lithium salt
- Example FF wherein the substrate was first contacted with a conversion coating comprising a lanthanide series element (yttrium) and subsequently contacted with a sealing solution comprising a lithium salt, demonstrated greater than a 50% reduction in the number of corrosion pits after both 3 days and 7 days exposure to neutral salt spray in comparison to both Examples AA (substrate only contacted with the sealing solution) and CC (substrate only contacted with the lanthanide containing conversion coating).
- a conversion coating comprising a lanthanide series element (yttrium)
- a sealing solution comprising a lithium salt
- Example GG wherein the substrate was first contacted with a conversion coating comprising a lanthanide series element (both cerium and yttrium) and subsequently contacted with a sealing solution comprising a lithium salt, demonstrated a reduced number of corrosion pits after 7 days exposure to neutral salt spray in comparison to both Example AA (substrate only contacted with the sealing solution) and Example 1 (substrate only contacted with the lanthanide containing conversion coating).
- a conversion coating comprising a lanthanide series element (both cerium and yttrium) and subsequently contacted with a sealing solution comprising a lithium salt
- Example HH wherein the substrate was first contacted with a conversion coating comprising a lanthanide series element (cerium) and subsequently contacted with a sealing solution comprising a lithium salt, demonstrated a reduced number of corrosion pits after 7 days exposure to neutral salt spray in comparison to both Example AA (substrate only contacted with the sealing solution) and Example 4 (substrate only contacted with the lanthanide containing conversion coating). Additionally, the number of pits were further reduced relative to Example DD and the detectable level of cerium on the substrate was measurably greater than that measured for Example DD.
- a conversion coating comprising a lanthanide series element (cerium)
- a sealing solution comprising a lithium salt
- Example KK wherein the substrate was first contacted with a conversion coating comprising a Group IVB series element (zirconium) and subsequently contacted with a sealing solution comprising a lithium salt, demonstrated a reduced number of corrosion pits after 7 days exposure to neutral salt spray in comparison to both Examples II (substrate only contacted with the sealing solution) and JJ (substrate only contacted with the Group IVB containing conversion coating).
- a conversion coating comprising a Group IVB series element (zirconium) and subsequently contacted with a sealing solution comprising a lithium salt
- Example MM wherein the substrate was first contacted with a conversion coating comprising a Group IVB series element (titanium) and subsequently contacted with a sealing solution comprising a lithium salt, demonstrated a reduced number of corrosion pits after 7 days exposure to neutral salt spray in comparison to both Examples II (substrate only contacted with the sealing solution) and LL (substrate only contacted with the Group IVB containing conversion coating).
- a conversion coating comprising a Group IVB series element (titanium) and subsequently contacted with a sealing solution comprising a lithium salt
- Aluminum 6111 panels (from ACT Test Panels, LLC) were cut to 4′′ ⁇ 6′′ sample size. The bottom 3′′ of the panels were sanded with P320 grit silicon carbide paper (available from 3M) on a 6′′ random orbital palm sander (Advanced Tool Design Model-ATD-2088). Half-sanding the panel surface served to determine any corrosion performance difference between as-milled (unsanded) and sanded substrates. Surface sanding or abrasion is conducted in the field to promote adhesion of subsequent paint applications.
- Chemkleen 2010LP/181ALP bath Composed of 1.25 vol. % of Chemkleen 2010LP (a phosphate-free alkaline cleaner available from PPG) and 0.125 vol. % of Chemkleen 181 ALP (a phosphate-free blended surfactant additive, available from PPG) in deionized water) in a stainless steel spray tank using vee-jet nozzles at 10 to 15 psi, for two minutes at 120° F. This was followed by immersion rinse in DI water for 15 seconds, and final spray rinse with DI water for 15 seconds.
- the first set of panels were pretreated with Zircobond 1.5, a zirconium-conversion commercially available from PPG Industries, Inc.
- a 5-gallon bath was prepared as per manufacturer's instruction to yield a pH of 4.72, a zirconium concentration of 200 ppm, and a free fluoride concentration of 101 ppm.
- the panels were pretreated by immersion into the conversion bath at 80° F. with low agitation, for 2 minutes.
- the panels were spray rinsed with DI water for 20 to 30 seconds, and air dried using a Hi-Velocity handheld blow-dryer made by Oster® (model number 078302-300-000) on high-setting at a temperature of about 50-55° C. until fully dry (about 3 to 5 minutes).
- the second set of panels were pretreated with a lithium hydroxide conversion composition.
- the lithium hydroxide conversion composition was composed of 0.15 wt. % of lithium carbonate (available from Acros Organics) in deionized water.
- the panels were pretreated by immersion into a 3-gallon bath at ambient temperature for 1 minute, without agitation. Immediately after conversion, the panels were air dried using a Hi-Velocity handheld blow-dryer made by Oster® (model number 078302-300-000) on high-setting at a temperature of about 50-55° C. until fully dry (about 3 to 5 minutes).
- the third set of panels were pretreated with a lithium carbonate conversion composition.
- the lithium carbonate conversion composition was composed of 0.15 wt. % of lithium carbonate (available from Acros Organics) in deionized water.
- the panels were pretreated by immersion into a 3-gallon bath at ambient temperature for 1 minute, without agitation. Immediately after conversion, the panels were air dried using a Hi-Velocity handheld blow-dryer made by Oster® (model number 078302-300-000) on high-setting at a temperature of about 50-55° C. until fully dry (about 3 to 5 minutes).
- the pretreated panels were electrocoated with cationic ED6280Z paint (available from PPG) using rectifier (Xantrex Model XFR600-2).
- a coating dry film thickness of 0.8 mil was achieved by passing a 24.5 C, 21.5 C, and 21.0 C charge for the zirconium, lithium hydroxide, and lithium carbonate conversioned panels, respectively, at a current limit of 0.5 A, and an applied electrical potential of 220 V after a 30 second ramp time using a direct current rectifier (Xantrex Model XFR600-2).
- the ED6280Z paint bath was maintained at 90° F., with a stir rate of 340 rpm.
- the electrocoated panels were spray rinsed with DI water.
- the panels were baked in an electric oven (Despatch Model LFD-1-42) at 177° C. for 25 minutes.
- the coating thickness was measured using a Permascope (Fischer Technology Inc. Model FMP40C).
- Corrosion damage was measured as the perpendicular distance from the scribe to tip of the filament or blister. Each panel provided two sets of five measurements: a set from the top legs for the as-milled surface, and another set from the bottom legs for the sanded surface. Measurements were taken from the five longest corrosion sites. The average corrosion damage was calculated based on a total often measurements from duplicate panels. All readings were measured using a Fowler Sylvac digital caliper Model S 235.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Treatment Of Metals (AREA)
- Sealing Material Composition (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Chemically Coating (AREA)
- Analysing Materials By The Use Of Radiation (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
Description
- This application claims priority to U.S. Provisional Application No. 62/374,188, filed on Aug. 12, 2016 and entitled “Sealing Composition” and to U.S. Provisional Application No. 62/374,199, filed Aug. 12, 2016 and entitled “Pretreatment Composition”, both of which are incorporated in their entirety herein by reference.
- The present invention relates to sealing compositions and methods for treating a metal substrate. The present invention also relates to a coated metal substrate.
- The oxidation and degradation of metals used in aerospace, commercial, and private industries are a serious and costly problem. To prevent the oxidation and degradation of the metals used in these applications, an inorganic protective coating can be applied to the metal surface. This inorganic protective coating, also referred to as a conversion coating, may be the only coating applied to the metal, or the coating can be an intermediate coating to which subsequent coatings are applied.
- Chromate based coatings are currently used as inorganic conversion coatings because they provide corrosion resistant properties and adhesion for application of subsequent coatings. However, due to environmental concerns over chromium based compounds in the environment, there is a need for an environmentally safer replacement for chromate based conversion coatings. There is also a need for environmentally safer conversion coatings that can provide corrosion resistance to an underlying metal surface and adhesion to subsequently applied coatings.
- Cerium and other rare earth element containing coatings have been identified as potential replacements for chromate based coatings in metal finishing. These coatings include cerium and other rare earth element containing coatings that are formed by various processes such as immersion, electroplating from a cerium nitrate solution, plating from an acidic cerium chloride containing solution and an oxidant (at elevated temperatures), as well as multi-step processes, and electrolytic and non-electrolytic processes having a sealing step.
- However, at least some of the coatings prepared using these compositions and methods do not perform as well as those formed using chromate treatments and/or can develop corrosion and/or pits on the surface. Further, at least some of the cerium and other rare earth element-containing coatings known in the art can also suffer from one or more of the following disadvantages: (1) a tendency of the rare earth element to precipitate in solution away from the metal surface in the form of a sludge-like material; (2) difficulty in obtaining a uniform coating which does not tend to over-coat and exhibit poor adhesion to the substrate; (3) the necessity to use multiple steps and extensive periods of time to deposit a coating; and (4) the necessity to use specific conversions and solution compositions in order to coat multiply alloys, especially aluminum 2024 alloys.
- Therefore, there is a need for a method of treating a substrate that can replace chromate based conversion coatings and that overcomes several of the deficiencies, disadvantages and undesired parameters of known replacements for chromate based conversion coatings.
- Disclosed herein is a method of treating a substrate comprising: contacting at least a portion of the substrate surface with a sealing composition comprising a lithium cation. According to the present invention, the method may further comprise contacting at least a portion of the substrate with a lanthanide series metal cation, a Group IIIB metal cation, a Group IVB metal cation, or a combination thereof. According to the invention, the sealing composition may be applied to provide a layer of the dried sealing composition having a thickness of 5 nm to 550 nm.
- Also disclosed is a system for treating a substrate comprising: a conversion composition for treating at a least a portion of the substrate, the conversion composition comprising a lanthanide series metal cation, a Group IIIB metal cation, a Group IVB metal cation, or a combination thereof; and a sealing composition for treating at least a portion of the substrate, the sealing composition comprising a lithium cation.
- Also disclosed are substrates obtainable by the system and/or methods.
-
FIG. 1 shows a schematic illustrating thickness of a layer of the sealing composition on a substrate surface. - Disclosed herein according to the invention is a system for treating a substrate comprising, or in some instances, consisting essentially of, or in some instances, consisting of, a sealing composition comprising, or in instances, consisting essentially of, or in some instances, consisting of, a lithium cation. The system may further comprise, or in some instances consist essentially of, or in some instances, consist of, a conversion composition comprising, or in some instances, consisting essentially of, or in some instances, consisting of, a lanthanide series metal cation, a Group IIIB metal cation, a Group IVB metal cation, or a combination thereof. In some instances, the system may further comprise, or consist essentially of, or consist of, a cleaning composition and/or a deoxidizer.
- As mentioned above, also disclosed herein is a method of treating a substrate comprising, or in some instances, consisting essentially of, or in some instances, consisting of: contacting at least a portion of the substrate surface with a sealing composition comprising, or in some instances, consisting essentially of, or in some instances, consisting of, a lithium cation. According to the invention, the method may also comprise, or in some instances, consist essentially of, or in some instances, consist of, contacting at least a portion of the substrate surface with a conversion composition comprising, or in some instances, consisting essentially of, or in some instances, consisting of, a lanthanide series metal cation, a Group IIIB metal cation, a Group IVB metal cation, or a combination thereof.
- As described herein, a substrate treated with the system and/or method of the present invention may comprise, or in some instances consist essentially of, or in some instances, consist of, a layer formed from the sealing composition comprising a lithium cation. In some instances, the substrate may further comprise a film or a layer formed from the conversion composition comprising cations of a lanthanide series metal, a Group IIIB metal, and/or a Group IVB metal.
- Suitable substrates that may be used in the present invention include metal substrates, metal alloy substrates, and/or substrates that have been metallized, such as nickel plated plastic. According to the present invention, the metal or metal alloy can comprise or be steel, aluminum, zinc, nickel, and/or magnesium. For example, the steel substrate could be cold rolled steel, hot rolled steel, electrogalvanized steel, and/or hot dipped galvanized steel. Aluminum alloys of the 1XXX, 2XXX, 3XXX, 4XXX, 5XXX, 6XXX, or 7XXX series as well as clad aluminum alloys also may be used as the substrate. Aluminum alloys may comprise 0.01% by weight copper to 10% by weight copper. Aluminum alloys which are treated may also include castings, such as 1XX.X, 2XX.X, 3XX.X, 4XX.X, 5XX.X, 6XX.X, 7XX.X, 8XX.X, or 9XX.X (e.g.: A356.0). Magnesium alloys of the AZ31B, AZ91C, AM60B, or EV31A series also may be used as the substrate. The substrate used in the present invention may also comprise titanium and/or titanium alloys, zinc and/or zinc alloys, and/or nickel and/or nickel alloys. According to the present invention, the substrate may comprise a portion of a vehicle such as a vehicular body (e.g., without limitation, door, body panel, trunk deck lid, roof panel, hood, roof and/or stringers, rivets, landing gear components, and/or skins used on an aircraft) and/or a vehicular frame. As used herein, “vehicle” or variations thereof includes, but is not limited to, civilian, commercial and military aircraft, and/or land vehicles such as cars, motorcycles, and/or trucks.
- The sealing composition may comprise a lithium cation. The lithium cation may be in the form of a lithium salt. In addition, the sealing composition also may further comprise at least one Group IA metal cation other than lithium, a Group VB metal cation, and/or Group VIB metal cation. The at least one Group IA metal cation other than lithium, a Group VB metal cation, and/or Group VIB metal cation may be in the form of a salt. Nonlimiting examples of anions suitable for forming a salt with the lithium, Group IA cations other than lithium, Group VB cations, and/or Group VIB cations include carbonates, hydroxides, nitrates, halogens, sulfates, phosphates and silicates (e.g., orthosilicates and metasilicates) such that the metal salt may comprise a carbonate, an hydroxide, a nitrate, a halide, a sulfate, a phosphate, a silicate (e.g., orthosilicate or metasilicate), a permanganate, a chromate, a vanadate, a molybdate, and/or a perchlorate.
- According to the present invention, the metal salts of the sealing composition (i.e., the salts of lithium, Group IA metals other than lithium, Group VB, and/or Group VIB) each may be present in the sealing composition in an amount of at least 25 ppm, such as at least 150 ppm, such as at least 500 ppm (calculated as total compound) based on total weight of the sealing composition, and in some instances, no more than 30000 ppm, such as no more than 2000 ppm, such as no more than 1500 ppm (calculated as total compound) based on total weight of the sealing composition. According to the present invention, the metal salts of the sealing composition (i.e., the salts of lithium, Group IA metals other than lithium, Group VB, and/or Group VIB) each may be present in the sealing composition in an amount of 25 ppm to 30000 ppm, such as 150 ppm to 2000 ppm, such as 500 ppm to 1500 (calculated as total compound) based on total weight of the sealing composition.
- According to the present invention, the lithium cation, the Group IA cation other than lithium, the Group VB metal cation, and the Group VIB metal cation each may be present in the sealing composition in an amount of at least 5 ppm, such as at least 50 ppm, such as at least 150 ppm, such as at least 250 ppm (calculated as cation) based on total weight of the sealing composition, and in some instances, may be present in an amount of no more than 5500 ppm, such as no more than 1200 ppm, such as no more than 1000 ppm, such as no more than 500 ppm, (calculated as cation) based on total weight of the sealing composition. In some instances, according to the present invention, the lithium cation, the Group IA cation other than lithium, the Group VB metal cation, and the Group VIB metal cation each may be present in the sealing composition in an amount of 5 ppm to 5500 ppm, such as 50 ppm to 1000 ppm, (calculated as cation) based on total weight of the sealing composition, such as 150 ppm to 500 ppm.
- According to the present invention, the lithium salt of the present invention may comprise an inorganic lithium salt, an organic lithium salt, or combinations thereof. According to the present invention, the anion and the cation of the lithium salt both may be soluble in water. According to the present invention, for example, the lithium salt may have a solubility constant in water at a temperature of 25° C. (K; 25° C.) of at least 1×10−11, such as least 1×10−4, and in some instances, may be no more than 5×10+2. According to the present invention, the lithium salt may have a solubility constant in water at a temperature of 25° C. (K; 25° C.) of 1×10−11 to 5×10+2, such as 1×10−4 to 5×10+2. As used herein, “solubility constant” means the product of the equilibrium concentrations of the ions in a saturated aqueous solution of the respective lithium salt. Each concentration is raised to the power of the respective coefficient of ion in the balanced equation. The solubility constants for various salts can be found in the Handbook of Chemistry and Physics.
- According to the present invention, the sealing composition of the present invention may an include oxidizing agent, such as hydrogen peroxide, persulfates, perchlorates, sparged oxygen, bromates, peroxi-benzoates, ozone, and the like, or combinations thereof. For example, the sealing composition may comprise 0.1 wt % to 15 wt % of an oxidizing agent based on total weight of the sealing composition, such as 2 wt % to 10 wt %, such as 6 wt % to 8 wt %. Alternatively, according to the present invention, the sealing composition may be substantially free, or in some cases, essentially free, or in some cases, completely free, of an oxidizing agent.
- According to the present invention, the sealing composition may exclude Group IIA metal cations or Group IIA metal-containing compounds, including but not limited to calcium. Non-limiting examples of such materials include Group IIA metal hydroxides, Group IIA metal nitrates, Group IIA metal halides, Group IIA metal sulfamates, Group IIA metal sulfates, Group IIA carbonates and/or Group IIA metal carboxylates. When a sealing composition and/or a coating or a layer, respectively, formed from the same is substantially free, essentially free, or completely free of a Group IIA metal cation, this includes Group IIA metal cations in any form, such as, but not limited to, the Group IIA metal-containing compounds listed above.
- According to the present invention, the sealing composition may exclude chromium or chromium-containing compounds. As used herein, the term “chromium-containing compound” refers to materials that include hexavalent chromium. Non-limiting examples of such materials include chromic acid, chromium trioxide, chromic acid anhydride, dichromate salts, such as ammonium dichromate, sodium dichromate, potassium dichromate, and calcium, barium, magnesium, zinc, cadmium, and strontium dichromate. When a sealing composition and/or a coating or a layer, respectively, formed from the same is substantially free, essentially free, or completely free of chromium, this includes chromium in any form, such as, but not limited to, the hexavalent chromium-containing compounds listed above.
- Thus, optionally, according to the present invention, the present sealing compositions and/or coatings or layers, respectively, deposited from the same may be substantially free, may be essentially free, and/or may be completely free of one or more of any of the elements or compounds listed in the preceding paragraph. A sealing composition and/or coating or layer, respectively, formed from the same that is substantially free of chromium or derivatives thereof means that chromium or derivatives thereof are not intentionally added, but may be present in trace amounts, such as because of impurities or unavoidable contamination from the environment. In other words, the amount of material is so small that it does not affect the properties of the sealing composition; in the case of chromium, this may further include that the element or compounds thereof are not present in the sealing compositions and/or coatings or layers, respectively, formed from the same in such a level that it causes a burden on the environment. The term “substantially free” means that the sealing compositions and/or coating or layers, respectively, formed from the same contain less than 10 ppm of any or all of the elements or compounds listed in the preceding paragraph, based on total weight of the composition or the layer, respectively, if any at all. The term “essentially free” means that the sealing compositions and/or coatings or layers, respectively, formed from the same contain less than 1 ppm of any or all of the elements or compounds listed in the preceding paragraph, if any at all. The term “completely free” means that the sealing compositions and/or coatings or layers, respectively, formed from the same contain less than 1 ppb of any or all of the elements or compounds listed in the preceding paragraph, if any at all.
- According to the present invention, the sealing composition may, in some instances, exclude phosphate ions or phosphate-containing compounds and/or the formation of sludge, such as aluminum phosphate, iron phosphate, and/or zinc phosphate, formed in the case of using a treating agent based on zinc phosphate. As used herein, “phosphate-containing compounds” include compounds containing the element phosphorous such as ortho phosphate, pyrophosphate, metaphosphate, tripolyphosphate, organophosphonates, and the like, and can include, but are not limited to, monovalent, divalent, or trivalent cations such as: sodium, potassium, calcium, zinc, nickel, manganese, aluminum and/or iron. When a composition and/or a layer or coating comprising the same is substantially free, essentially free, or completely free of phosphate, this includes phosphate ions or compounds containing phosphate in any form.
- Thus, according to the present invention, sealing composition and/or layers deposited from the same may be substantially free, or in some cases may be essentially free, or in some cases may be completely free, of one or more of any of the ions or compounds listed in the preceding paragraph. A sealing composition and/or layers deposited from the same that is substantially free of phosphate means that phosphate ions or compounds containing phosphate are not intentionally added, but may be present in trace amounts, such as because of impurities or unavoidable contamination from the environment. In other words, the amount of material is so small that it does not affect the properties of the composition; this may further include that phosphate is not present in the sealing compositions and/or layers deposited from the same in such a level that they cause a burden on the environment. The term “substantially free” means that the sealing compositions and/or layers deposited from the same contain less than 5 ppm of any or all of the phosphate anions or compounds listed in the preceding paragraph, based on total weight of the composition or the layer, respectively, if any at all. The term “essentially free” means that the sealing compositions and/or layers comprising the same contain less than 1 ppm of any or all of the phosphate anions or compounds listed in the preceding paragraph. The term “completely free” means that the sealing compositions and/or layers comprising the same contain less than 1 ppb of any or all of the phosphate anions or compounds listed in the preceding paragraph, if any at all.
- According to the present invention, the sealing composition may, in some instances, exclude fluoride or fluoride sources. As used herein, “fluoride sources” include monofluorides, bifluorides, fluoride complexes, and mixtures thereof known to generate fluoride ions. When a composition and/or a layer or coating comprising the same is substantially free, essentially free, or completely free of fluoride, this includes fluoride ions or fluoride sources in any form, but does not include unintentional fluoride that may be present in a bath as a result of, for example, carry-over from prior treatment baths in the processing line, municipal water sources (e.g.: fluoride added to water supplies to prevent tooth decay), fluoride from a pretreated substrate, or the like. That is, a bath that is substantially free, essentially free, or completely free of fluoride, may have unintentional fluoride that may be derived from these external sources, even though the composition used to make the bath prior to use on the processing line was substantially free, essentially free, or completely free of fluoride.
- For example, the sealing composition may be substantially free of any fluoride-sources, such as ammonium and alkali metal fluorides, acid fluorides, fluoroboric, fluorosilicic, fluorotitanic, and fluorozirconic acids and their ammonium and alkali metal salts, and other inorganic fluorides, nonexclusive examples of which are: zinc fluoride, zinc aluminum fluoride, titanium fluoride, zirconium fluoride, nickel fluoride, ammonium fluoride, sodium fluoride, potassium fluoride, and hydrofluoric acid, as well as other similar materials known to those skilled in the art.
- Fluoride present in the sealing composition that is not bound to metals ions such as Group IVB metal ions, or hydrogen ion, defined herein as “free fluoride,” may be measured as an operational parameter in the sealing composition bath using, for example, an Orion Dual Star Dual Channel Benchtop Meter equipped with a fluoride ion selective electrode (“ISE”) available from Thermoscientific, the Symphony® Fluoride Ion Selective Combination Electrode supplied by VWR International, or similar electrodes. See, e.g., Light and Cappuccino, Determination of fluoride in toothpaste using an ion-selective electrode, J. Chem. Educ., 52:4, 247-250, April 1975. The fluoride ISE may be standardized by immersing the electrode into solutions of known fluoride concentration and recording the reading in millivolts, and then plotting these millivolt readings in a logarithmic graph. The millivolt reading of an unknown sample can then be compared to this calibration graph and the concentration of fluoride determined. Alternatively, the fluoride ISE can be used with a meter that will perform the calibration calculations internally and thus, after calibration, the concentration of the unknown sample can be read directly.
- Fluoride ion is a small negative ion with a high charge density, so in aqueous solution it is frequently complexed with metal ions having a high positive charge density, such as Group IVB metal ions, or with hydrogen ion. Fluoride anions in solution that are ionically or covalently bound to metal cations or hydrogen ion are defined herein as “bound fluoride.” The fluoride ions thus complexed are not measurable with the fluoride ISE unless the solution they are present in is mixed with an ionic strength adjustment buffer (e.g.: citrate anion or EDTA) that releases the fluoride ions from such complexes. At that point (all of) the fluoride ions are measurable by the fluoride ISE, and the measurement is known as “total fluoride”. Alternatively, the total fluoride can be calculated by comparing the weight of the fluoride supplied in the sealer composition by the total weight of the composition.
- According to the present invention, the treatment composition may, in some instances, be substantially free, or in some instances, essentially free, or in some instances, completely free, of cobalt ions or cobalt-containing compounds. As used herein, “cobalt-containing compounds” include compounds, complexes or salts containing the element cobalt such as, for example, cobalt sulfate, cobalt nitrate, cobalt carbonate and cobalt acetate. When a composition and/or a layer or coating comprising the same is substantially free, essentially free, or completely free of cobalt, this includes cobalt ions or compounds containing cobalt in any form.
- According to the present invention, the treatment composition may, in some instances, be substantially free, or in some instances, essentially free, or in some instances, completely free, of vanadium ions or vanadium-containing compounds. As used herein, “vanadium-containing compounds” include compounds, complexes or salts containing the element vanadium such as, for example, vanadates and decavanadates that include counterions of alkali metal or ammonium cations, including, for example, sodium ammonium decavanadate. When a composition and/or a layer or coating comprising the same is substantially free, essentially free, or completely free of vanadium, this includes vanadium ions or compounds containing vanadium in any form.
- According to the present invention, the sealing composition may optionally further contain an indicator compound, so named because it indicates, for example, the presence of a chemical species, such as a metal ion, the pH of a composition, and the like. An “indicator”, “indicator compound”, and like terms as used herein refer to a compound that changes color in response to some external stimulus, parameter, or condition, such as the presence of a metal ion, or in response to a specific pH or range of pHs.
- The indicator compound used according to the present invention can be any indicator known in the art that indicates the presence of a species, a particular pH, and the like. For example, a suitable indicator may be one that changes color after forming a metal ion complex with a particular metal ion. The metal ion indicator is generally a highly conjugated organic compound. A “conjugated compound” as used herein, and as will be understood by those skilled in the art, refers to a compound having two double bonds separated by a single bond, for example two carbon-carbon double bonds with a single carbon-carbon bond between them. Any conjugated compound can be used according to the present invention.
- Similarly, the indicator compound can be one in which the color changes upon change of the pH; for example, the compound may be one color at an acidic or neutral pH and change color in an alkaline pH, or vice versa. Such indicators are well known and widely commercially available. An indicator that “changes color upon transition from a first pH to a second pH” (i.e., from a first pH to a second pH that is more or less acidic or alkaline) therefore has a first color (or is colorless) when exposed to a first pH and changes to a second color (or goes from colorless to colored) upon transition to a second pH (i.e., one that is either more or less acidic or alkaline than the first pH). For example, an indicator that “changes color upon transition to a more alkaline pH (or less acidic pH) goes from a first color/colorless to a second color/color when the pH transitions from acidic/neutral to alkaline. For example, an indicator that “changes color upon transition to a more acidic pH (or less alkaline pH) goes from a first color/colorless to a second color/color when the pH transitions from alkaline/neutral to acidic.
- Non-limiting examples of such indicator compounds include methyl orange, xylenol orange, catechol violet, bromophenol blue, green and purple, eriochrome black T, Celestine blue, hematoxylin, calmagite, gallocyanine, and combinations thereof. Optionally, the indicator compound may comprise an organic indicator compound that is a metal ion indicator. Nonlimiting examples of indicator compounds include those found in Table 1. Fluorescent indicators, which will emit light in certain conditions, can also be used according to the present invention, although the use of a fluorescent indicator also may be specifically excluded. That is, alternatively, conjugated compounds that exhibit fluorescence are specifically excluded. As used herein, “fluorescent indicator” and like terms refer to compounds, molecules, pigments, and/or dyes that will fluoresce or otherwise exhibit color upon exposure to ultraviolet or visible light. To “fluoresce” will be understood as emitting light following absorption of shorter wavelength light or other electromagnetic radiation. Examples of such indicators, often referred to as “tags,” include acridine, anthraquinone, coumarin, diphenylmethane, diphenylnaphthlymethane, quinoline, stilbene, triphenylmethane, anthracine and/or molecules containing any of these moieties and/or derivatives of any of these such as rhodamines, phenanthridines, oxazines, fluorones, cyanines and/or acridines.
- According to the present invention, the conjugated compound useful as indicator may for example comprise catechol violet, as shown in Table 1. Catechol violet (CV) is a sulfone phthalein dye made from condensing two moles of pyrocatechol with one mole of o-sulfobenzoic acid anhydride. It has been found that CV has indicator properties and when incorporated into compositions having metal ions, it forms complexes, making it useful as a complexiometric reagent. As the composition containing the CV chelates metal ions coming from the metal substrate (i.e., those having bi- or higher valence), a generally blue to blue-violet color is observed.
- 1 Xylenol orange, as shown in Table 1 may likewise be employed in the compositions according to the present invention. It has been found that xylenol orange has metal ion (i.e., those having bi- or higher valence) indicator properties and when incorporated into compositions having metal ions, it forms complexes, making it useful as a complexiometric reagent. As the composition containing the xylenol orange chelates metal ions, a solution of xylenol orange turns from red to a generally blue color.
- According to the present invention, the indicator compound may be present in the sealing composition in an amount of at least 0.01 g/1000 g sealing composition, such as at least 0.05 g/1000 g sealing composition, and in some instances, no more than 3 g/1000 g sealing composition, such as no more than 0.3 g/1000 g sealing composition. According to the present invention, the indicator compound may be present in the sealing composition in an amount of 0.01 g/1000 g sealing composition to 3 g/1000 g sealing composition, such as 0.05 g/1000 g sealing composition to 0.3 g/1000 g sealing composition.
- According to the present invention, the indicator compound changing color in response to a certain external stimulus provides a benefit when using the sealing composition in that it can serve, for example, as a visual indication that a substrate has been treated with the composition. For example, a sealing composition comprising an indicator that changes color when exposed to a metal ion that is present in the substrate will change color upon complexing with metal ions in that substrate; this allows the user to see that the substrate has been contacted with the composition. Similar benefits can be realized by depositing an alkaline or acid layer on a substrate and contacting the substrate with a composition of the present invention that changes color when exposed to an alkaline or acidic pH.
- Optionally, the sealing composition of the present invention may further comprise a nitrogen-containing heterocyclic compound. The nitrogen-containing heterocyclic compound may include cyclic compounds having 1 nitrogen atom, such as pyrroles, and azole compounds having 2 or more nitrogen atoms, such as pyrazoles, imidazoles, triazoles, tetrazoles and pentazoles, 1 nitrogen atom and 1 oxygen atom, such as oxazoles and isoxazoles, or 1 nitrogen atom and 1 sulfur atom, such as thiazoles and isothiazoles. Nonlimiting examples of suitable azole compounds include 2,5-dimercapto-1,3,4-thiadiazole (CAS: 1072-71-5), 1H-benzotriazole (CAS: 95-14-7), 1H-1,2,3-triazole (CAS: 288-36-8), 2-amino-5-mercapto-1,3,4-thiadiazole (CAS: 2349-67-9), also named 5-amino-1,3,4-thiadiazole-2-thiol, and 2-amino-1,3,4-thiadiazole (CAS: 4005-51-0). In some embodiments, for example, the azole compound comprises 2,5-dimercapto-1,3,4-thiadiazole. Additionally, according to the present invention, the nitrogen-containing heterocyclic compound may be in the form of a salt, such as a sodium salt.
- The nitrogen-containing heterocyclic compound may be present in the sealing composition at a concentration of at least 0.0005 g per liter of composition, such as at least 0.0008 g per liter of composition, such as at least 0.002 g per liter of composition, and in some instances, may be present in the sealing composition in an amount of no more than 3 g per liter of composition, such as no more than 0.2 g per liter of composition, such as no more than 0.1 g per liter of composition. According to the present invention, the nitrogen-containing heterocyclic compound may be present in the sealing composition (if at all) at a concentration of 0.0005 g per liter of composition to 3 g per liter of composition, such as 0.0008 g per liter of composition to 0.2 g per liter of composition, such as 0.002 g per liter of composition to 0.1 g per liter of composition.
- According to the present invention, the sealing composition may comprise an aqueous medium and optionally may contain other materials such as at least one organic solvent. Nonlimiting examples of suitable such solvents include propylene glycol, ethylene glycol, glycerol, low molecular weight alcohols, and the like. When present, if at all, the organic solvent may be present in the sealing composition in an amount of at least 1 g solvent per liter of sealing composition, such as at least about 2 g solvent per liter of sealing solution, and in some instances, may be present in an amount of no more than 40 g solvent per liter of sealing composition, such as no more than 20 g solvent per liter of sealing solution. According to the present invention, the organic solvent may be present in the sealing composition, if at all, in an amount of 1 g solvent per liter of sealing composition to 40 g solvent per liter of sealing composition, such as 2 g solvent per liter of sealing composition to 20 g solvent per liter of sealing composition.
- According to the present invention, the pH of the sealing composition may be at least 9.5, such as at least 10, such as at least 11, and in some instances may be no higher than 12.5, such as no higher than 12, such as no higher than 11.5. According to the present invention, the pH of the sealing composition may be 9.5 to 12.5, such as 10 to 12, such as 11 to 11.5. The pH of the sealing composition may be adjusted using, for example, any acid and/or base as is necessary. According to the present invention, the pH of the sealing composition may be maintained through the inclusion of an acidic material, including carbon dioxide, water soluble and/or water dispersible acids, such as nitric acid, sulfuric acid, and/or phosphoric acid. According to the present invention, the pH of the sealing composition may be maintained through the inclusion of a basic material, including water soluble and/or water dispersible bases, including carbonates such as Group I carbonates, Group II carbonates, hydroxides such as sodium hydroxide, potassium hydroxide, or ammonium hydroxide, ammonia, and/or amines such as triethylamine, methylethyl amine, or mixtures thereof.
- As mentioned above, the sealing composition may comprise a carrier, often an aqueous medium, so that the composition is in the form of a solution or dispersion of the lithium cation in the carrier. According to the present invention, the solution or dispersion may be brought into contact with the substrate by any of a variety of known techniques, such as dipping or immersion, spraying, intermittent spraying, dipping followed by spraying, spraying followed by dipping, brushing, or roll-coating. According to the invention, the solution or dispersion when applied to the metal substrate may be at a temperature ranging from 40° F. to about 160° F., such as 60° F. to 110° F. For example, the process of contacting the metal substrate with the sealing composition may be carried out at ambient or room temperature. The contact time is often from about 1 second to about 15 minutes, such as about 5 seconds to about 2 minutes.
- According to the present invention, following the contacting with the sealing composition, the substrate optionally may be air dried at room temperature or may be dried with hot air, for example, by using an air knife, by flashing off the water by brief exposure of the substrate to a high temperature, such as by drying the substrate in an oven at 15° C. to 100° C., such as 20° C. to 90° C., or in a heater assembly using, for example, infrared heat, such as for 10 minutes at 70° C., or by passing the substrate between squeegee rolls. According to the present invention, the substrate surface may be partially, or in some instances, completely dried prior to any subsequent contact of the substrate surface with any water, solutions, compositions, or the like. As used herein with respect to a substrate surface, “completely dry” or “completely dried” means there is no moisture on the substrate surface visible to the human eye.
- Optionally, according to the present invention, following the contacting with the sealing composition, the substrate optionally is not rinsed or contacted with any aqueous solutions prior to contacting at least a portion of the substrate surface with subsequent treatment compositions to form films, layers, and/or coatings thereon (described below).
- Optionally, according to the present invention, following the contacting with the sealing composition, the substrate optionally may be contacted with tap water, deionized water, RO water and/or any aqueous solution known to those of skill in the art of substrate treatment, wherein such water or aqueous solution may be at a temperature of room temperature (60° F.) to 212° F. The substrate then optionally may be dried, for example air dried or dried with hot air as described in the preceding paragraph such that the substrate surface may be partially, or in some instances, completely dried prior to any subsequent contact of the substrate surface with any water, solutions, compositions, or the like.
- According to the present invention, the thickness of the layer formed by the treatment composition may for instance be up to 550 nm, such as 5 nm to 550 nm, such as 10 nm to 400 nm, such as 25 nm to 250 nm. Thickness of layer formed from the treatment composition can be determined using a handful of analytical techniques including, but not limited to XPS (x-ray photoelectron spectroscopy) depth profiling or TEM (transmission electron microscopy). As used herein, “thickness,” when used with respect to a layer formed by the treatment composition of the present invention, refers to either (a) a layer formed above the original air/substrate interface, (b) a modified layer formed below the pretreatment/substrate interface, or (c) a combination of (a) and (b), as illustrated in
FIG. 1 . Although modified layer (b) is shown extending to the pretreatment/substrate interface inFIG. 1 , an intervening layer may be present between the modified layer (b) and the pretreatment/substrate interface. Likewise, (c), a combination of (a) and (b), is not limited to a continuous layer and may include multiple layers with intervening layers therebetween, and the measurement of the thickness of layer (c) may exclude the intervening layers. - According to the present invention, the substrate having the layer formed from the sealing composition may have at least a 50% reduction in the number of pits on the substrate surface compared to a substrate that does not have a layer formed from the sealing composition thereon following 3 day exposure in neutral salt spray cabinet operated according to ASTM B117.
- Additionally, according to the present invention, the substrate having the layer formed from the sealing composition may have at least a 50% reduction in the number of pits on the substrate surface compared to a substrate that does not have a layer formed from the sealing composition thereon following 7 day exposure in neutral salt spray cabinet operated according to ASTM B117.
- According to the present invention, at least a portion of the substrate surface may be cleaned and/or deoxidized prior to contacting at least a portion of the substrate surface with a sealing composition described above, in order to remove grease, dirt, and/or other extraneous matter. At least a portion of the surface of the substrate may be cleaned by physical and/or chemical means, such as mechanically abrading the surface and/or cleaning/degreasing the surface with commercially available alkaline or acidic cleaning agents that are well known to those skilled in the art. Examples of alkaline cleaners suitable for use in the present invention include Chemkleen™ 166HP, 166M/C, 177, 490MX, 2010LP, and Surface Prep 1 (SPI), Ultrax 32, Ultrax 97, Ultrax 29, and Ultrax92D, each of which are commercially available from PPG Industries, Inc. (Cleveland, Ohio), and any of the DFM Series, RECC 1001, and 88X1002 cleaners commercially available from PRC-DeSoto International, Sylmar, Calif.), and Turco 4215-NCLT and Ridolene (commercially available from Henkel Technologies, Madison Heights, Mich.). Such cleaners are often preceded or followed by a water rinse, such as with tap water, distilled water, or combinations thereof.
- As mentioned above, according to the present invention, at least a portion of the cleaned substrate surface may be deoxidized, mechanically and/or chemically. As used herein, the term “deoxidize” means removal of the oxide layer found on the surface of the substrate in order to promote uniform deposition of the conversion composition (described below), as well as to promote the adhesion of the conversion composition coating to the substrate surface. Suitable deoxidizers will be familiar to those skilled in the art. A typical mechanical deoxidizer may be uniform roughening of the substrate surface, such as by using a scouring or cleaning pad. Typical chemical deoxidizers include, for example, acid-based deoxidizers such as phosphoric acid, nitric acid, fluoroboric acid, sulfuric acid, chromic acid, hydrofluoric acid, and ammonium bifluoride, or Amchem 7/17 deoxidizers (available from Henkel Technologies, Madison Heights, Mich.), OAKITE DEOXIDIZER LNC (commercially available from Chemetall), TURCO DEOXIDIZER 6 (commercially available from Henkel), or combinations thereof. Often, the chemical deoxidizer comprises a carrier, often an aqueous medium, so that the deoxidizer may be in the form of a solution or dispersion in the carrier, in which case the solution or dispersion may be brought into contact with the substrate by any of a variety of known techniques, such as dipping or immersion, spraying, intermittent spraying, dipping followed by spraying, spraying followed by dipping, brushing, or roll-coating. According to the present invention, the skilled artisan will select a temperature range of the solution or dispersion, when applied to the metal substrate, based on etch rates, for example, at a temperature ranging from 50° F. to 150° F. (10° C. to 66° C.), such as from 70° F. to 130° F. (21° C. to 54° C.), such as from 80° F. to 120° F. (27° C. to 49° C.). The contact time may be from 30 seconds to 20 minutes, such as 1 minute to 15 minutes, such as 90 seconds to 12 minutes, such as 3 minutes to 9 minutes.
- Following the cleaning and/or deoxidizing step(s), the substrate optionally may be rinsed with tap water, deionized water, and/or an aqueous solution of rinsing agents in order to remove any residue. According to the present invention, the wet substrate surface may be treated with a conversion composition (described below) and/or a sealing composition (described above), or the substrate may be dried prior to treating the substrate surface, such as air dried, for example, by using an air knife, by flashing off the water by brief exposure of the substrate to a high temperature, such as 15° C. to 100° C., such as 20° C. to 90° C., or in a heater assembly using, for example, infrared heat, such as for 10 minutes at 70° C., or by passing the substrate between squeegee rolls.
- As mentioned above, at least a portion of the substrate surface optionally may be contacted with a conversion composition prior to or after being contacted with the sealing composition described above. The conversion composition may be spontaneously depositable or electrodepositable. As used herein, “spontaneously depositable,” when used with respect to the conversion composition, refers to a composition that is capable of reacting with and chemically altering the substrate surface and binding to it to form a protective layer in the absence of an externally applied voltage. As used herein, an “electrodepositable,” when used with respect to the conversion composition, refers to a composition containing a non-elemental metal, i.e. a metal-containing compound, complex, ion or the like wherein the metal is not in elemental form, that is capable of reacting with and chemically altering the substrate surface and binding to it to form a protective layer upon the introduction of an externally applied voltage. Such an electrodepositable conversion composition may be applied using any methods or parameters known to those skilled in the art.
- According to the present invention, the conversion composition may comprise a lanthanide series element cation, a Group IIIB metal cation and/or a Group IVB metal cation. The conversion composition also may further comprise an ion of a Group IIA metal, a Group VB metal, a Group VIB metal, a Group VIIB metal, and/or a Group XII metal (together with the lanthanide series cation, the Group IIIB metal cation, and/or the Group IVB metal cation, referred to collectively herein as “conversion composition metal cations”).
- According to the present invention, the salts of the conversion composition metal cations may be present in the conversion composition in an amount of at least 5 ppm, such as at least 50 ppm, such as at least 100 ppm, (calculated as metal salt) based on total weight of the conversion composition, and in some instances, may be present in an amount of no more than 25000 ppm, such as no more than 9000 ppm, such as no more than 1500 (calculated as metal salt) based on total weight of the conversion composition. According to the present invention, the salt of the conversion composition metal cations may be present in the conversion composition in an amount of 5 ppm to 25000 ppm (calculated as metal salt) based on total weight of the conversion composition, such as 50 ppm to 9000 ppm, such as 100 ppm to 1500 ppm.
- According to the present invention, the conversion composition metal cation may be present in the conversion composition in an amount of at least 5 ppm, such as at least 150 ppm, such as at least 300 ppm, (calculated as metal cation) based on total weight of the conversion composition, and in some instances may be present in the conversion composition in an amount of no more than 25,000 ppm, such as no more than 12,500 ppm, such as no more than 10,000 ppm, (calculated as metal cation) based on total weight of the conversion composition. According to the present invention, the conversion composition metal cation may be present in the conversion composition in an amount of 5 ppm to 25,000 ppm, such as 150 ppm to 12,500 ppm, such as 300 ppm to 10,000 ppm, (calculated as metal cation) based on total weight of the conversion composition.
- According to the present invention, the lanthanide series element cation may, for example, comprise cerium, praseodymium, terbium, or combinations thereof; the Group IIA metal cation may comprise magnesium; the Group IIIB metal cation may comprise yttrium, scandium, or combinations thereof; the Group IVB metal cation may comprise zirconium, titanium, hafnium, or combinations thereof; the Group VB metal cation may comprise vanadium; the Group VIB metal may comprise molybdenum; the Group VIIB metal cation may comprise trivalent or hexavalent chromium or manganese; and the Group XII metal cation may comprise zinc.
- For example, the Group IIIB metal and/or Group IVB metal cation used in the conversion composition may be a compound of zirconium, titanium, hafnium, yttrium, scandium, or a mixture thereof. Suitable compounds of zirconium include, but are not limited to, hexafluorozirconic acid, alkali metal and ammonium salts thereof, ammonium zirconium carbonate, zirconyl nitrate, zirconyl sulfate, zirconium carboxylates and zirconium hydroxy carboxylates, such as zirconium acetate, zirconium oxalate, ammonium zirconium glycolate, ammonium zirconium lactate, ammonium zirconium citrate, and mixtures thereof. Suitable compounds of titanium include, but are not limited to, fluorotitanic acid and its salts. A suitable compound of hafnium includes, but is not limited to, hafnium nitrate. Suitable compounds of yttrium include, but are not limited to, yttrium halides.
- According to the present invention, the Group IIIB metal cation and/or the Group IVB metal cation may be present in the conversion composition in a total amount of at least 20 ppm metal (calculated as metal cation), based on total weight of the conversion composition, such as at least 50 ppm metal, or, in some cases, at least 70 ppm metal. According to the present invention, the Group IIIB metal cation and/or the Group IVB metal cation may be present in the conversion composition in a total amount of no more than 1000 ppm metal (calculated as metal cation), based on total weight of the conversion composition, such as no more than 600 ppm metal, or, in some cases, no more than 300 ppm metal. According to the present invention, the Group IIIB metal cation and/or the Group IVB metal cation may be present in the conversion composition in a total amount of 20 ppm metal to 1000 ppm metal (calculated as metal cation), based on total weight of the conversion composition, such as from 50 ppm metal to 600 ppm metal, such as from 70 ppm metal to 300 ppm metal. As used herein, the term “total amount,” when used with respect to the amount of Group IIIB metal cation and/or Group IVB metal cation, means the sum of all Group IIIB and/or Group IV metal cations present in the conversion composition.
- According to the present invention, the salts of the conversion composition metal cations may be present in the conversion composition in an amount of at least 5 ppm, such as at least 50 ppm, such as at least 100 ppm, (calculated as metal salt) based on total weight of the conversion composition, and in some instances, may be present in an amount of no more than 25000 ppm, such as no more than 9000 ppm, such as no more than 1500 (calculated as total metal salt) based on total weight of the conversion composition. According to the present invention, the salt of the conversion composition metal cations may be present in the conversion composition in an amount of 5 ppm to 25000 ppm, such as 50 ppm to 9000 ppm, such as 100 ppm to 1500 ppm.
- According to the present invention, the conversion composition metal cation may be present in the conversion composition in an amount of at least 5 ppm, such as at least 150 ppm, such as at least 300 ppm, (calculated as metal cation) based on total weight of the conversion composition, and in some instances may be present in the conversion composition in an amount of no more than 25,000 ppm, such as no more than 12,500 ppm, such as no more than 10,000 ppm, (calculated as metal cation) based on total weight of the conversion composition. According to the present invention, the conversion composition metal cation may be present in the conversion composition in an amount of 5 ppm to 25,000 ppm, such as 150 ppm to 12,500 ppm, such as 300 ppm to 10,000 ppm (calculated as metal cation) based on total weight of the conversion composition.
- According to the present invention, the conversion composition also may comprise an electropositive metal ion. As used herein, the term “electropositive metal ion” refers to metal ions that will be reduced by the metal substrate being treated when the conversion solution contacts the surface of the metallic substrate. As will be appreciated by one skilled in the art, the tendency of chemical species to be reduced is called the reduction potential, is expressed in volts, and is measured relative to the standard hydrogen electrode, which is arbitrarily assigned a reduction potential of zero. The reduction potential for several elements is set forth in Table 2 below (according to the CRC 82nd Edition, 2001-2002). An element or ion is more easily reduced than another element or ion if it has a voltage value, E*, in the following table, that is more positive than the elements or ions to which it is being compared.
-
TABLE 2 Element Reduction half-cell reaction Voltage, E* Potassium K+ + e → K −2.93 Calcium Ca2+ + 2e → Ca −2.87 Sodium Na+ + e → Na −2.71 Magnesium Mg2+ + 2e → Mg −2.37 Aluminum Al3+ + 3e → Al −1.66 Zinc Zn2+ + 2e → Zn −0.76 Iron Fe2+ + 2e → Fe −0.45 Nickel Ni2+ + 2e → Ni −0.26 Tin Sn2+ + 2e → Sn −0.14 Lead Pb2+ + 2e → Pb −0.13 Hydrogen 2H+ + 2e → H2 −0.00 Copper Cu2+ + 2e → Cu 0.34 Mercury Hg2 2+ + 2e → 2Hg 0.80 Silver Ag+ + e → Ag 0.80 Gold Au3+ + 3e → Au 1.50 - Thus, as will be apparent, when the metal substrate comprises one of the materials listed earlier, such as cold rolled steel, hot rolled steel, steel coated with zinc metal, zinc compounds, or zinc alloys, hot-dipped galvanized steel, galvanealed steel, steel plated with zinc alloy, aluminum alloys, aluminum plated steel, aluminum alloy plated steel, magnesium and magnesium alloys, suitable electropositive metals for deposition thereon include, for example, nickel, copper, silver, and gold, as well mixtures thereof.
- According to the present invention, when the electropositive metal comprises copper, both soluble and insoluble compounds may serve as a source of copper ions in the conversion compositions. For example, the supplying source of copper ions in the conversion composition may be a water soluble copper compound. Specific examples of such compounds include, but are not limited to, copper cyanide, copper potassium cyanide, copper sulfate, copper nitrate, copper pyrophosphate, copper thiocyanate, disodium copper ethylenediaminetetraacetate tetrahydrate, copper bromide, copper oxide, copper hydroxide, copper chloride, copper fluoride, copper gluconate, copper citrate, copper lauroyl sarcosinate, copper formate, copper acetate, copper propionate, copper butyrate, copper lactate, copper oxalate, copper phytate, copper tartrate, copper malate, copper succinate, copper malonate, copper maleate, copper benzoate, copper salicylate, copper aspartate, copper glutamate, copper fumarate, copper glycerophosphate, sodium copper chlorophyllin, copper fluorosilicate, copper fluoroborate and copper iodate, as well as copper salts of carboxylic acids in the homologous series formic acid to decanoic acid, copper salts of polybasic acids in the series oxalic acid to suberic acid, and copper salts of hydroxycarboxylic acids, including glycolic, lactic, tartaric, malic and citric acids.
- When copper ions supplied from such a water-soluble copper compound are precipitated as an impurity in the form of copper sulfate, copper oxide, etc., it may be desirable to add a complexing agent that suppresses the precipitation of copper ions, thus stabilizing them as a copper complex in the composition.
- According to the present invention, the copper compound may be added as a copper complex salt such as K3Cu(CN)4 or Cu-EDTA, which can be present stably in the conversion composition on its own, but it is also possible to form a copper complex that can be present stably in the conversion composition by combining a complexing agent with a compound that is difficult to solubilize on its own. Examples thereof include a copper cyanide complex formed by a combination of CuCN and KCN or a combination of CuSCN and KSCN or KCN, and a Cu-EDTA complex formed by a combination of CuSO4 and EDTA.2Na.
- With regard to the complexing agent, a compound that can form a complex with copper ions can be used; examples thereof include inorganic compounds such as cyanide compounds and thiocyanate compounds, and polycarboxylic acids, and specific examples thereof include ethylenediaminetetraacetic acid, salts of ethylenediaminetetraacetic acid such as dihydrogen disodium ethylenediaminetetraacetate dihydrate, aminocarboxylic acids such as nitrilotriacetic acid and iminodiacetic acid, oxycarboxylic acids such as citric acid and tartaric acid, succinic acid, oxalic acid, ethylenediaminetetramethylenephosphonic acid, and glycine, and organophosphonates such as 1-hydroxethylidene-1,1-diphosphonic acid (commercially available from Italmatch Chemicals as Dequest 2010).
- According to the present invention, the electropositive metal ion may be present in the conversion composition in an amount of at least 2 ppm (calculated as metal ion) based on the total weight of the conversion composition, such as at least 4 ppm, such as at least 6 ppm, such as at least 8 ppm, such as at least 10 ppm. According to the present invention, the electropositive metal ion may be present in the conversion composition in an amount of no more than 100 ppm (calculated as metal ion) based on the total weight of the conversion composition, such as no more than 80 ppm, such as no more than 60 ppm, such as no more than 40 ppm, such as no more than 20 ppm. According to the present invention, the electropositive metal ion may be present in the conversion composition in an amount of from 2 ppm to 100 ppm (calculated as metal ion) based on the total weight of the conversion composition, such as from 4 ppm to 80 ppm, such as from 6 ppm to 60 ppm, such as from 8 ppm to 40 ppm, such as from 10 ppm to 20 ppm. The amount of electropositive metal ion in the conversion composition can range between the recited values inclusive of the recited values.
- According to the present invention, a source of fluoride may be present in the conversion composition. As used herein the amount of fluoride disclosed or reported in the conversion composition is referred to as “free fluoride,” as measured in part per millions of fluoride. Free fluoride is defined above as being able to be measured by a fluoride-selective ISE. In addition to free fluoride, a conversion may also contain “bound fluoride, which is described above. The sum of the concentrations of the bound and free fluoride equal the total fluoride, which can be determined as described above. The total fluoride in the conversion composition can be supplied by hydrofluoric acid, as well as alkali metal and ammonium fluorides or hydrogen fluorides. Additionally, total fluoride in the conversion composition may be derived from Group IVB metals present in the conversion composition, including, for example, hexafluorozirconic acid or hexafluorotitanic acid. Other complex fluorides, such as H2SiF6 or HBF4, can be added to the conversion composition to supply total fluoride. The skilled artisan will understand that the presence of free fluoride in the conversion bath can impact conversion deposition and etching of the substrate, hence it is critical to measure this bath parameter. The levels of free fluoride will depend on the pH and the addition of chelators into the conversion bath and indicates the degree of fluoride association with the metal ions/protons present in the conversion bath. For example, conversion compositions of identical total fluoride levels can have different free fluoride levels which will be influenced by the pH and chelators present in the conversion solution.
- According to the present invention, the total fluoride of the conversion composition may be present in an amount of at least 25 ppm, based on a total weight of the conversion composition, such as at least 100 ppm fluoride, such as at least 200 ppm fluoride. According to the present invention, the total fluoride of the conversion composition may be present in an amount of no more than 5000 ppm, based on a total weight of the conversion composition, such as no more than 2000 ppm fluoride, such as no more than 1000 ppm fluoride. According to the present invention, the total fluoride of the conversion composition may be present in an amount of 10 ppm fluoride to 5000 ppm fluoride, based on a total weight of the conversion composition, such as 100 ppm fluoride to 2000 ppm, such as no more than 200 ppm fluoride to 1000 ppm fluoride.
- According to the present invention, the free fluoride of the conversion composition may be present in an amount of at least 15 ppm, based on a total weight of the conversion composition, such as at least 50 ppm free fluoride, such as at least 100 ppm free fluoride, such as at least 200 ppm free fluoride. According to the present invention, the free fluoride of the conversion composition may be present in an amount of no more than 2500 ppm, based on a total weight of the conversion composition, such as no more than 1000 ppm free fluoride, such as no more than 500 ppm free fluoride, such as no more than 250 ppm free fluoride. According to the present invention, the free fluoride of the conversion composition may be present in an amount of 15 ppm free fluoride to 2500 ppm free fluoride, based on a total weight of the conversion composition, such as 50 ppm fluoride to 1000 ppm, such as no more than 200 ppm free fluoride to 500 ppm free fluoride, such as no more than 100 ppm free fluoride to 250 ppm free fluoride.
- According to the present invention, the conversion composition also may comprise a lithium cation. According to the invention, the conversion composition may further comprise an anion that may be suitable for forming a salt with the lithium cation. Non-limiting examples of suitable lithium salts include lithium nitrate, lithium sulfate, lithium fluoride, lithium chloride, lithium hydroxide, lithium carbonate, lithium iodide, and combinations thereof.
- According to the present invention, the lithium cation may be present in the conversion composition in an amount of at least 2 ppm (as lithium cation) based on a total weight of the conversion composition, such as at least 5 ppm, such as at least 25 ppm, such as at least 75 ppm, and in some instances, may be present in amount of no more than 500 ppm, based on a total weight of the conversion composition, such as no more than 250 ppm, such as no more than 125 ppm, such as no more than 100 ppm. According to the present invention, the lithium cation may be present in the conversion composition in an amount of 2 ppm to 500 ppm (as lithium cation) based on a total weight of the conversion composition, such as 5 ppm to 250 ppm, such as 25 ppm to 125 ppm, such as 75 ppm to 100 ppm. The amount of lithium cation in the conversion composition can range between the recited values inclusive of the recited values.
- According to the present invention, the conversion composition may also comprise a molybdenum cation. According to the invention, the conversion composition may further comprise an anion that may be suitable for forming a salt with the molybdenum cation. Non-limiting examples of suitable molybdenum salts include sodium molybdate, calcium molybdate, potassium molybdate, ammonium molybdate, molybdenum chloride, molybdenum acetate, molybdenum sulfamate, molybdenum formate, molybdenum lactate, and combinations thereof.
- According to the present invention, molybdenum cation may be present in the conversion composition in an amount of at least 5 ppm (as molybdenum cation) based on a total weight of the conversion composition, such as at least 25 ppm, such as 100 ppm, and in some instances, may be present in the conversion composition in an amount of no more than 500 ppm, based on total weight of the conversion composition, such as no more than 250 ppm, such as no more than 150 ppm. According to the present invention, molybdenum may be present in the conversion composition in an amount of 5 ppm to 500 ppm (as molybdenum cation) based on total weight of the conversion composition, such as 25 ppm to 250 ppm, such as 100 ppm to 150 ppm. The amount of molybdenum in the conversion composition can range between the recited values inclusive of the recited values.
- According to the present invention, the conversion composition may further comprise an anion that may be suitable for forming a salt with the conversion composition metal cations, such as a halogen, a nitrate, a sulfate, a phosphate, a silicate (orthosilicates and metasilicates), carbonates, hydroxides, and the like. According to the present invention, the conversion composition metal salt may be present in the conversion composition in an amount of at least 50 ppm (calculated as metal salt) based on total weight of the conversion composition, such as at least 1000 ppm, and in some instances, may be present in an amount of no more than 30,000 ppm, such as no more than 2000 ppm. According to the present invention, the conversion composition metal salt may be present in an amount of 50 ppm to 30,000 ppm, such as 1000 ppm to 2000 ppm (calculated as metal salt) based on total weight of the conversion composition.
- According to the present invention, the halogen may be present in the conversion composition, if at all, in an amount of at least 5 ppm (calculated as anion) based on total weight of the conversion composition, such as at least 50 ppm, such as at least 150 ppm, such as at least 500 ppm, and may be present in an amount of no more than 25,000 ppm (calculated as anion) based on total weight of the conversion composition, such as no more than 18,500 ppm, such as no more than 4000 ppm, such as no more than 2000 ppm. According to the present invention, the halogen may be present in the conversion composition, if at all, in an amount of 5 ppm to 25,000 ppm (calculated as anion) based on total weight of the conversion composition, such as 50 ppm to 18,500 ppm, such as 150 ppm to 4000, such as 500 ppm to 2000 ppm.
- According to the present invention, the nitrate may be present in the conversion composition, if at all, in an amount of at least 2 ppm (calculated as anion) based on total weight of the conversion composition, such as at least 50 ppm, such as at least 250 ppm, and may be present in an amount of no more than 10,000 ppm (calculated as anion) based on total weight of the conversion composition, such as no more than 5000 ppm, such as no more than 2500 ppm. According to the present invention, the halogen may be present in the conversion composition, if at all, in an amount of 2 ppm to 10,000 ppm (calculated as anion) based on total weight of the conversion composition, such as 50 ppm to 5000 ppm, such as 250 ppm to 2500 ppm.
- According to the present invention, the conversion composition may, in some instances, comprise an oxidizing agent. Non-limiting examples of the oxidizing agent include peroxides, persulfates, perchlorates, hypochlorite, nitric acid, sparged oxygen, bromates, peroxi-benzoates, ozone, or combinations thereof.
- According to the present invention, the oxidizing agent may be present, if at all, in an amount of at least 100 ppm, such as at least 500 ppm, based on total weight of the conversion composition, and in some instances, may be present in an amount of no more than 13,000 ppm, such as no more than 3000 ppm, based on total weight of the conversion composition. In some instances, the oxidizing agent may be present in the conversion composition, if at all, in an amount of 100 ppm to 13,000 ppm, such as 500 ppm to 3000 ppm, based on total weight of the conversion composition.
- According to the present invention, the conversion composition may exclude chromium or chromium-containing compounds. As used herein, the term “chromium-containing compound” refers to materials that include hexavalent chromium. Non-limiting examples of such materials include chromic acid, chromium trioxide, chromic acid anhydride, dichromate salts, such as ammonium dichromate, sodium dichromate, potassium dichromate, and calcium, barium, magnesium, zinc, cadmium, and strontium dichromate. When a conversion composition and/or a coating or a layer, respectively, formed from the same is substantially free, essentially free, or completely free of chromium, this includes chromium in any form, such as, but not limited to, the hexavalent chromium-containing compounds listed above.
- Thus, optionally, according to the present invention, the present conversion compositions and/or coatings or layers, respectively, deposited from the same may be substantially free, may be essentially free, and/or may be completely free of one or more of any of the elements or compounds listed in the preceding paragraph. A conversion composition and/or coating or layer, respectively, formed from the same that is substantially free of chromium or derivatives thereof means that chromium or derivatives thereof are not intentionally added, but may be present in trace amounts, such as because of impurities or unavoidable contamination from the environment. In other words, the amount of material is so small that it does not affect the properties of the conversion composition; in the case of chromium, this may further include that the element or compounds thereof are not present in the conversion compositions and/or coatings or layers, respectively, formed from the same in such a level that it causes a burden on the environment. The term “substantially free” means that the conversion compositions and/or coating or layers, respectively, formed from the same contain less than 10 ppm of any or all of the elements or compounds listed in the preceding paragraph, based on total weight of the composition or the layer, respectively, if any at all. The term “essentially free” means that the conversion compositions and/or coatings or layers, respectively, formed from the same contain less than 1 ppm of any or all of the elements or compounds listed in the preceding paragraph, if any at all. The term “completely free” means that the conversion compositions and/or coatings or layers, respectively, formed from the same contain less than 1 ppb of any or all of the elements or compounds listed in the preceding paragraph, if any at all.
- According to the present invention, the conversion composition may, in some instances, exclude phosphate ions or phosphate-containing compounds and/or the formation of sludge, such as aluminum phosphate, iron phosphate, and/or zinc phosphate, formed in the case of using a treating agent based on zinc phosphate. As used herein, “phosphate-containing compounds” include compounds containing the element phosphorous such as ortho phosphate, pyrophosphate, metaphosphate, tripolyphosphate, organophosphonates, and the like, and can include, but are not limited to, monovalent, divalent, or trivalent cations such as: sodium, potassium, calcium, zinc, nickel, manganese, aluminum and/or iron. When a composition and/or a layer or coating comprising the same is substantially free, essentially free, or completely free of phosphate, this includes phosphate ions or compounds containing phosphate in any form.
- Thus, according to the present invention, conversion composition and/or layers deposited from the same may be substantially free, or in some cases may be essentially free, or in some cases may be completely free, of one or more of any of the ions or compounds listed in the preceding paragraph. A conversion composition and/or layers deposited from the same that is substantially free of phosphate means that phosphate ions or compounds containing phosphate are not intentionally added, but may be present in trace amounts, such as because of impurities or unavoidable contamination from the environment. In other words, the amount of material is so small that it does not affect the properties of the composition; this may further include that phosphate is not present in the conversion compositions and/or layers deposited from the same in such a level that they cause a burden on the environment. The term “substantially free” means that the conversion compositions and/or layers deposited from the same contain less than 5 ppm of any or all of the phosphate anions or compounds listed in the preceding paragraph, based on total weight of the composition or the layer, respectively, if any at all. The term “essentially free” means that the conversion compositions and/or layers comprising the same contain less than 1 ppm of any or all of the phosphate anions or compounds listed in the preceding paragraph. The term “completely free” means that the conversion compositions and/or layers comprising the same contain less than 1 ppb of any or all of the phosphate anions or compounds listed in the preceding paragraph, if any at all.
- According to the present invention, the pH of the conversion composition may be 1.0 to 4.5, such as 3 to 4, and may be adjusted using, for example, any acid and/or base as is necessary. According to the present invention, the pH of the conversion composition may be maintained through the inclusion of an acidic material, including water soluble and/or water dispersible acids, such as nitric acid, sulfuric acid, and/or phosphoric acid. According to the present invention, the pH of the composition may be maintained through the inclusion of a basic material, including water soluble and/or water dispersible bases, such as sodium hydroxide, sodium carbonate, potassium hydroxide, ammonium hydroxide, ammonia, and/or amines such as triethylamine, methylethyl amine, or mixtures thereof.
- The conversion composition may comprise an aqueous medium and may optionally contain other materials such as nonionic surfactants and auxiliaries conventionally used in the art of conversion compositions. In the aqueous medium, water dispersible organic solvents, for example, alcohols with up to about 8 carbon atoms such as methanol, isopropanol, and the like, may be present; or glycol ethers such as the monoalkyl ethers of ethylene glycol, diethylene glycol, or propylene glycol, and the like. When present, water dispersible organic solvents are typically used in amounts up to about ten percent by volume, based on the total volume of aqueous medium.
- Other optional materials include surfactants that function as defoamers or substrate wetting agents. Anionic, cationic, amphoteric, and/or nonionic surfactants may be used. Defoaming surfactants may optionally be present at levels up to 1 weight percent, such as up to 0.1 percent by weight, and wetting agents are typically present at levels up to 2 percent, such as up to 0.5 percent by weight, based on the total weight of the conversion composition.
- Optionally, according to the present invention, the conversion composition and/or films deposited or formed therefrom may further comprise silicon in amounts of at least 10 ppm, based on total weight of the conversion composition, such as at least 20 ppm, such as at least 50 ppm. According to the present invention, the conversion composition and/or films deposited or formed therefrom may comprise silicon in amounts of less than 500 ppm, based on total weight of the conversion composition, such as less than 250 ppm, such as less than 100 ppm. According to the present invention, the conversion composition and/or films deposited or formed therefrom may comprise silicon in amounts of 10 ppm to 500 ppm, based on total weight of the conversion composition, such as 20 ppm to 250 ppm, such as 50 ppm to 100 ppm. Alternatively, the conversion composition of the present invention and/or films deposited or formed therefrom may be substantially free, or, in some cases, completely free of silicon.
- The conversion composition may comprise a carrier, often an aqueous medium, so that the composition is in the form of a solution or dispersion of the lanthanide and/or Group IIIB metal in the carrier. In these embodiments, the solution or dispersion may be brought into contact with the substrate by any of a variety of known techniques, such as dipping or immersion, spraying, intermittent spraying, dipping followed by spraying, spraying followed by dipping, brushing, or roll-coating. According to the invention, the solution or dispersion when applied to the metal substrate is at a temperature ranging from 40° F. to 160° F., such as 60° F. to 110° F., such as 70° F. to 90° F. For example, the conversion process may be carried out at ambient or room temperature. The contact time is often from 30 seconds to 15 minutes, such as 4 minutes to 10 minutes.
- According to the present invention, following the contacting with the conversion composition, the substrate optionally may be air dried at room temperature or may be dried with hot air, for example, by using an air knife, by flashing off the water by brief exposure of the substrate to a high temperature, such as by drying the substrate in an oven at 15° C. to 100° C., such as 20° C. to 90° C., or in a heater assembly using, for example, infrared heat, such as for 10 minutes at 70° C., or by passing the substrate between squeegee rolls. According to the present invention, following the contacting with the conversion composition, the substrate optionally may be rinsed with tap water, deionized water, and/or an aqueous solution of rinsing agents in order to remove any residue and then optionally may be dried, for example air dried or dried with hot air as described in the preceding sentence.
- According to the present invention, the level of the lanthanide, Group IIIB metal, and/or Group IVB metal in the film formed on the substrate surface from the conversion composition is at least 100 counts greater than on a surface of a substrate that does not have the film thereon as measured by X-ray fluorescence (measured using X-Met 7500, Oxford Instruments; operating parameters 60 second timed assay, 15 Kv, 45 μA, filter 3, T(p)=1.5 μs for lanthanides, Group IIIB metals, and Group IVB metals except zirconium; operating parameters 60 second timed assay, 40 Kv, 10 μA, filter 4, T(p)=1.5 μs for zirconium).
- According to the present invention, the substrate having been contacted with the conversion composition and having the layer formed from the sealing composition has at least a 50% reduction in the number of pits on the substrate surface compared to a substrate having the film formed from the conversion composition or the layer formed from the sealing composition but not the film and the seal following 3 day exposure in neutral salt spray cabinet operated according to ASTM B117.
- According to the present invention, the substrate having the film formed from the conversion composition and the layer formed from the sealing composition has at least a 50% reduction in the number of pits on the substrate surface compared to a substrate having the film formed from the conversion composition or the layer formed from the sealing composition but not the film and the seal following 3 day exposure in neutral salt spray cabinet operated according to ASTM BI 17.
- According to the present invention, disclosed herein is a substrate comprising, or in some instances consisting essentially of, or in some instances consisting of, a layer having a thickness of 25 nm to 250 nm formed from a sealing composition comprising, or in some instances consisting essentially of, or in some instances, consisting of, a lithium source. According to the present invention, the substrate may comprise an aluminum alloy comprising copper in an amount of 1 percent by weight to 10 percent by weight.
- According to the present invention, disclosed herein is a substrate comprising, or in some instances consisting essentially of, or in some instances consisting of: a film formed from a conversion composition comprising, or in some cases consisting essentially of, or in some instances consisting of, a lanthanide, a Group IIIB metal, a Group IVB metal, or combinations thereof, wherein the level of the lanthanide, Group IIIB metal, and/or Group IVB metal in the film is at least 100 counts greater than on a surface of a substrate that does not have the film thereon as measured by X-ray fluorescence (measured using X-Met 7500, Oxford Instruments; operating parameters 60 second timed assay, 15 Kv, 45 μA, filter 3, T(p)=1.5 μs for lanthanides, Group IIIB metals, and Group IVB metals except zirconium; operating parameters 60 second timed assay, 40 Kv, 10 μA, filter 4, T(p)=1.5 μs for zirconium); and a layer formed from a sealing composition comprising, or in some instances consisting essentially of, or in some instances consisting of, a lithium source.
- According to the present invention, disclosed herein is a method of treating a substrate comprising, or in some instances consisting essentially of, or in some instances consisting of, contacting at least a portion of the substrate surface with a sealing composition comprising, or in some instances consisting essentially of, or in some instances, consisting of, a lithium source. According to the present invention, the substrate may comprise an aluminum alloy comprising copper in an amount of 1 percent by weight to 10 percent by weight.
- According to the present invention, disclosed herein is a method of treating a substrate, comprising, or in some instances consisting essentially of, or in some instances consisting of, (a) contacting at least a portion of the substrate surface with a conversion composition comprising, or in some instances consisting essentially of, or in some instances consisting of, a lanthanide, a Group IIIB metal, a Group IVB metal, or combinations thereof; and (b) contacting at least a portion of the substrate surface contacted with the conversion composition with a sealing composition comprising, or in some instances consisting essentially of, or in some instances consisting of, a lithium source.
- It has been surprisingly discovered that the combination contacting a substrate surface with a lanthanide-containing conversion composition and a lithium-containing sealing composition that includes either Group VB salt or a Group VIB salt further reduced the level of pitting on the substrate surface following 3 day exposure in neutral salt spray cabinet operated according to ASTM B117 compared to a substrate surface that has been contacted with the conversion composition and a sealing composition that does not include the Group VB salt or Group VIB salt. These results were unexpected.
- It also has been surprisingly discovered that the combination of a film formed from a lanthanide-containing conversion composition with a layer formed from a lithium-containing sealing composition results in at least a 50% reduction in the number of pits on the substrate surface compared to a substrate surface that has the conversion composition film or the sealing composition layer but not both following 7 day exposure in neutral salt spray cabinet operated according to ASTM BI 17. These results were unexpected.
- Notably, on sanded substrates, corrosion performance was markedly improved on when such sanded substrates were treated according to the system and method of the present invention.
- According to the present invention, after the substrate is contacted with the sealing composition, a coating composition comprising a film-forming resin may be deposited onto at least a portion of the surface of the substrate that has been contacted with the sealing composition. Any suitable technique may be used to deposit such a coating composition onto the substrate, including, for example, brushing, dipping, flow coating, spraying and the like. In some instances, however, as described in more detail below, such depositing of a coating composition may comprise an electrocoating step wherein an electrodepositable composition is deposited onto a metal substrate by electrodeposition. In certain other instances, as described in more detail below, such depositing of a coating composition comprises a powder coating step. In still other instances, the coating composition may be a liquid coating composition.
- According to the present invention, the coating composition may comprise a thermosetting film-forming resin or a thermoplastic film-forming resin. As used herein, the term “film-forming resin” refers to resins that can form a self-supporting continuous film on at least a horizontal surface of a substrate upon removal of any diluents or carriers present in the composition or upon curing at ambient or elevated temperature. Conventional film-forming resins that may be used include, without limitation, those typically used in automotive OEM coating compositions, automotive refinish coating compositions, industrial coating compositions, architectural coating compositions, coil coating compositions, and aerospace coating compositions, among others. As used herein, the term “thermosetting” refers to resins that “set” irreversibly upon curing or crosslinking, wherein the polymer chains of the polymeric components are joined together by covalent bonds. This property is usually associated with a cross-linking reaction of the composition constituents often induced, for example, by heat or radiation. Curing or crosslinking reactions also may be carried out under ambient conditions. Once cured or crosslinked, a thermosetting resin will not melt upon the application of heat and is insoluble in solvents. As used herein, the term “thermoplastic” refers to resins that comprise polymeric components that are not joined by covalent bonds and thereby can undergo liquid flow upon heating and are soluble in solvents.
- As previously indicated, according to the present invention, an electrodepositable coating composition comprising a water-dispersible, ionic salt group-containing film-forming resin that may be deposited onto the substrate by an electrocoating step wherein the electrodepositable coating composition is deposited onto the metal substrate by electrodeposition.
- The ionic salt group-containing film-forming polymer may comprise a cationic salt group containing film-forming polymer for use in a cationic electrodepositable coating composition. As used herein, the term “cationic salt group-containing film-forming polymer” refers to polymers that include at least partially neutralized cationic groups, such as sulfonium groups and ammonium groups, that impart a positive charge. The cationic salt group-containing film-forming polymer may comprise active hydrogen functional groups, including, for example, hydroxyl groups, primary or secondary amine groups, and thiol groups. Cationic salt group-containing film-forming polymers that comprise active hydrogen functional groups may be referred to as active hydrogen-containing, cationic salt group-containing film-forming polymers. Examples of polymers that are suitable for use as the cationic salt group-containing film-forming polymer include, but are not limited to, alkyd polymers, acrylics, polyepoxides, polyamides, polyurethanes, polyureas, polyethers, and polyesters, among others.
- The cationic salt group-containing film-forming polymer may be present in the cationic electrodepositable coating composition in an amount of 40% to 90% by weight, such as 50% to 80% by weight, such as 60% to 75% by weight, based on the total weight of the resin solids of the electrodepositable coating composition. As used herein, the “resin solids” include the ionic salt group-containing film-forming polymer, curing agent, and any additional water-dispersible non-pigmented component(s) present in the electrodepositable coating composition.
- Alternatively, the ionic salt group containing film-forming polymer may comprise an anionic salt group containing film-forming polymer for use in an anionic electrodepositable coating composition. As used herein, the term “anionic salt group containing film-forming polymer” refers to an anionic polymer comprising at least partially neutralized anionic functional groups, such as carboxylic acid and phosphoric acid groups that impart a negative charge. The anionic salt group-containing film-forming polymer may comprise active hydrogen functional groups. Anionic salt group-containing film-forming polymers that comprise active hydrogen functional groups may be referred to as active hydrogen-containing, anionic salt group-containing film-forming polymers.
- The anionic salt group-containing film-forming polymer may comprise base-solubilized, carboxylic acid group-containing film-forming polymers such as the reaction product or adduct of a drying oil or semi-drying fatty acid ester with a dicarboxylic acid or anhydride; and the reaction product of a fatty acid ester, unsaturated acid or anhydride and any additional unsaturated modifying materials which are further reacted with polyol. Also suitable are the at least partially neutralized interpolymers of hydroxy-alkyl esters of unsaturated carboxylic acids, unsaturated carboxylic acid and at least one other ethylenically unsaturated monomer. Still another suitable anionic electrodepositable resin comprises an alkyd-aminoplast vehicle, i.e., a vehicle containing an alkyd resin and an amine-aldehyde resin. Another suitable anionic electrodepositable resin composition comprises mixed esters of a resinous polyol. Other acid functional polymers may also be used such as phosphatized polyepoxide or phosphatized acrylic polymers. Exemplary phosphatized polyepoxides are disclosed in U.S. Patent Application Publication No. 2009-0045071 at [0004]-[0015] and U.S. patent application Ser. No. 13/232,093 at [0014]-[0040], the cited portions of which being incorporated herein by reference.
- The anionic salt group-containing film-forming polymer may be present in the anionic electrodepositable coating composition in an amount 50% to 90%, such as 55% to 80%, such as 60% to 75%, based on the total weight of the resin solids of the electrodepositable coating composition.
- The electrodepositable coating composition may further comprise a curing agent. The curing agent may react with the reactive groups, such as active hydrogen groups, of the ionic salt group-containing film-forming polymer to effectuate cure of the coating composition to form a coating. Non-limiting examples of suitable curing agents are at least partially blocked polyisocyanates, aminoplast resins and phenoplast resins, such as phenolformaldehyde condensates including allyl ether derivatives thereof.
- The curing agent may be present in the cationic electrodepositable coating composition in an amount of 10% to 60% by weight, such as 20% to 50% by weight, such as 25% to 40% by weight, based on the total weight of the resin solids of the electrodepositable coating composition. Alternatively, the curing agent may be present in the anionic electrodepositable coating composition in an amount of 10% to 50% by weight, such as 20% to 45% by weight, such as 25% to 40% by weight, based on the total weight of the resin solids of the electrodepositable coating composition.
- The electrodepositable coating composition may further comprise other optional ingredients, such as a pigment composition and, if desired, various additives such as fillers, plasticizers, anti-oxidants, biocides, UV light absorbers and stabilizers, hindered amine light stabilizers, defoamers, fungicides, dispersing aids, flow control agents, surfactants, wetting agents, or combinations thereof.
- The electrodepositable coating composition may comprise water and/or one or more organic solvent(s). Water can for example be present in amounts of 40% to 90% by weight, such as 50% to 75% by weight, based on total weight of the electrodepositable coating composition. If used, the organic solvents may typically be present in an amount of less than 10% by weight, such as less than 5% by weight, based on total weight of the electrodepositable coating composition. The electrodepositable coating composition may in particular be provided in the form of an aqueous dispersion. The total solids content of the electrodepositable coating composition may be from 1% to 50% by weight, such as 5% to 40% by weight, such as 5% to 20% by weight, based on the total weight of the electrodepositable coating composition. As used herein, “total solids” refers to the non-volatile content of the electrodepositable coating composition, i.e., materials which will not volatilize when heated to 110° C. for 15 minutes.
- The cationic electrodepositable coating composition may be deposited upon an electrically conductive substrate by placing the composition in contact with an electrically conductive cathode and an electrically conductive anode, with the surface to be coated being the cathode. Alternatively, the anionic electrodepositable coating composition may be deposited upon an electrically conductive substrate by placing the composition in contact with an electrically conductive cathode and an electrically conductive anode, with the surface to be coated being the anode. An adherent film of the electrodepositable coating composition is deposited in a substantially continuous manner on the cathode or anode, respectively, when a sufficient voltage is impressed between the electrodes. The applied voltage may be varied and can be, for example, as low as one volt to as high as several thousand volts, such as between 50 and 500 volts. Current density is usually between 1.0 ampere and 15 amperes per square foot (10.8 to 161.5 amperes per square meter) and tends to decrease quickly during the electrodeposition process, indicating formation of a continuous self-insulating film.
- Once the cationic or anionic electrodepositable coating composition is electrodeposited over at least a portion of the electroconductive substrate, the coated substrate is heated to a temperature and for a time sufficient to cure the electrodeposited coating on the substrate. For cationic electrodeposition, the coated substrate may be heated to a temperature ranging from 250° F. to 450° F. (121.1° C. to 232.2° C.), such as from 275° F. to 400° F. (135° C. to 204.4° C.), such as from 300° F. to 360° F. (149° C. to 180° C.). For anionic electrodeposition, the coated substrate may be heated to a temperature ranging from 200° F. to 450° F. (93° C. to 232.2° C.), such as from 275° F. to 400° F. (135° C. to 204.4° C.), such as from 300° F. to 360° F. (149° C. to 180° C.), such as 200° F. to 210.2° F. (93° C. to 99° C.). The curing time may be dependent upon the curing temperature as well as other variables, for example, the film thickness of the electrodeposited coating, level and type of catalyst present in the composition and the like. For example, the curing time can range from 10 minutes to 60 minutes, such as 20 to 40 minutes. The thickness of the resultant cured electrodeposited coating may range from 2 to 50 microns.
- Alternatively, as mentioned above, according to the present invention, after the substrate has been contacted with the sealing composition, a powder coating composition may then be deposited onto at least a portion of the surface of the substrate. As used herein, “powder coating composition” refers to a coating composition which is completely free of water and/or solvent. Accordingly, the powder coating composition disclosed herein is not synonymous to waterborne and/or solvent-borne coating compositions known in the art.
- According to the present invention, the powder coating composition may comprise (a) a film forming polymer having a reactive functional group; and (b) a curing agent that is reactive with the functional group. Examples of powder coating compositions that may be used in the present invention include the polyester-based ENVIROCRON line of powder coating compositions (commercially available from PPG Industries, Inc.) or epoxy-polyester hybrid powder coating compositions. Alternative examples of powder coating compositions that may be used in the present invention include low temperature cure thermosetting powder coating compositions comprising (a) at least one tertiary aminourea compound, at least one tertiary aminourethane compound, or mixtures thereof, and (b) at least one film-forming epoxy-containing resin and/or at least one siloxane-containing resin (such as those described in U.S. Pat. No. 7,470,752, assigned to PPG Industries, Inc. and incorporated herein by reference); curable powder coating compositions generally comprising (a) at least one tertiary aminourea compound, at least one tertiary aminourethane compound, or mixtures thereof, and (b) at least one film-forming epoxy-containing resin and/or at least one siloxane-containing resin (such as those described in U.S. Pat. No. 7,432,333, assigned to PPG Industries, Inc. and incorporated herein by reference); and those comprising a solid particulate mixture of a reactive group-containing polymer having a Tg of at least 30° C. (such as those described in U.S. Pat. No. 6,797,387, assigned to PPG Industries, Inc. and incorporated herein by reference).
- After deposition of the powder coating composition, the coating is often heated to cure the deposited composition. The heating or curing operation is often carried out at a temperature in the range of from 150° C. to 200° C., such as from 170° C. to 190° C., for a period of time ranging from 10 to 20 minutes. According to the invention, the thickness of the resultant film is from 50 microns to 125 microns.
- As mentioned above, according to the present invention, the coating composition may be a liquid coating composition. As used herein, “liquid coating composition” refers to a coating composition which contains a portion of water and/or solvent. Accordingly, the liquid coating composition disclosed herein is synonymous to waterborne and/or solventborne coating compositions known in the art.
- According to the present invention, the liquid coating composition may comprise, for example, (a) a film forming polymer having a reactive functional group; and (b) a curing agent that is reactive with the functional group. In other examples, the liquid coating may contain a film forming polymer that may react with oxygen in the air or coalesce into a film with the evaporation of water and/or solvents. These film forming mechanisms may require or be accelerated by the application of heat or some type of radiation such as Ultraviolet or Infrared. Examples of liquid coating compositions that may be used in the present invention include the SPECTRACRON® line of solventbased coating compositions, the AQUACRON® line of waterbased coating compositions, and the RAYCRON® line of UV cured coatings (all commercially available from PPG Industries, Inc.).
- Suitable film forming polymers that may be used in the liquid coating composition of the present invention may comprise a (poly)ester, an alkyd, a (poly)urethane, an isocyanurate, a (poly)urea, a (poly)epoxy, an anhydride, an acrylic, a (poly)ether, a (poly)sulfide, a (poly)amine, a (poly)amide, (poly)vinyl chloride, (poly)olefin, (poly)vinylidene fluoride, (poly)siloxane, or combinations thereof.
- According to the present invention, the substrate that has been contacted with the sealing composition may also be contacted with a primer composition and/or a topcoat composition. The primer coat may be, for examples, chromate-based primers and advanced performance topcoats. According to the present invention, the primer coat can be a conventional chromate based primer coat, such as those available from PPG Industries, Inc. (product code 44GN072), or a chrome-free primer such as those available from PPG (DESOPRIME CA7502, DESOPRIME CA7521, Deft 02GN083, Deft 02GN084). Alternately, the primer coat can be a chromate-free primer coat, such as the coating compositions described in U.S. patent application Ser. No. 10/758,973, titled “CORROSION RESISTANT COATINGS CONTAINING CARBON”, and U.S. patent application Ser. Nos. 10/758,972, and 10/758,972, both titled “CORROSION RESISTANT COATINGS”, all of which are incorporated herein by reference, and other chrome-free primers that are known in the art, and which can pass the military requirement of MIL-PRF-85582 Class N or MIL-PRF-23377 Class N may also be used with the current invention.
- As mentioned above, the substrate of the present invention also may comprise a topcoat. As used herein, the term “topcoat” refers to a mixture of binder(s) which can be an organic or inorganic based polymer or a blend of polymers, typically at least one pigment, can optionally contain at least one solvent or mixture of solvents, and can optionally contain at least one curing agent. A topcoat is typically the coating layer in a single or multi-layer coating system whose outer surface is exposed to the atmosphere or environment, and its inner surface is in contact with another coating layer or polymeric substrate. Examples of suitable topcoats include those conforming to MIL-PRF-85285D, such as those available from PPG (Deft 03W127A and Deft 03GY292). According to the present invention, the topcoat may be an advanced performance topcoat, such as those available from PPG (Defthane® ELT™ 99GY001 and 99W009). However, other topcoats and advanced performance topcoats can be used in the present invention as will be understood by those of skill in the art with reference to this disclosure.
- According to the present invention, the metal substrate also may comprise a self-priming topcoat, or an enhanced self-priming topcoat. The term “self-priming topcoat”, also referred to as a “direct to substrate” or “direct to metal” coating, refers to a mixture of a binder(s), which can be an organic or inorganic based polymer or blend of polymers, typically at least one pigment, can optionally contain at least one solvent or mixture of solvents, and can optionally contain at least one curing agent. The term “enhanced self-priming topcoat”, also referred to as an “enhanced direct to substrate coating” refers to a mixture of functionalized fluorinated binders, such as a fluoroethylene-alkyl vinyl ether in whole or in part with other binder(s), which can be an organic or inorganic based polymer or blend of polymers, typically at least one pigment, can optionally contain at least one solvent or mixture of solvents, and can optionally contain at least one curing agent. Examples of self-priming topcoats include those that conform to TT-P-2756A. Examples of self-priming topcoats include those available from PPG (03W169 and 03GY369), and examples of enhanced self-priming topcoats include Defthane® ELT™/ESPT and product code number 97GY121, available from PPG. However, other self-priming topcoats and enhanced self-priming topcoats can be used in the coating system according to the present invention as will be understood by those of skill in the art with reference to this disclosure.
- According to the present invention, the self-priming topcoat and enhanced self-priming topcoat may be applied directly to the sealed substrate. The self-priming topcoat and enhanced self-priming topcoat can optionally be applied to an organic or inorganic polymeric coating, such as a primer or paint film. The self-priming topcoat layer and enhanced self-priming topcoat is typically the coating layer in a single or multi-layer coating system where the outer surface of the coating is exposed to the atmosphere or environment, and the inner surface of the coating is typically in contact with the substrate or optional polymer coating or primer.
- According to the present invention, the topcoat, self-priming topcoat, and enhanced self-priming topcoat can be applied to the sealed substrate, in either a wet or “not fully cured” condition that dries or cures over time, that is, solvent evaporates and/or there is a chemical reaction. The coatings can dry or cure either naturally or by accelerated means for example, an ultraviolet light cured system to form a film or “cured” paint. The coatings can also be applied in a semi or fully cured state, such as an adhesive.
- In addition, a colorant and, if desired, various additives such as surfactants, wetting agents or catalyst can be included in the coating composition (electrodepositable, powder, or liquid). As used herein, the term “colorant” means any substance that imparts color and/or other opacity and/or other visual effect to the composition. Example colorants include pigments, dyes and tints, such as those used in the paint industry and/or listed in the Dry Color Manufacturers Association (DCMA), as well as special effect compositions.
- In general, the colorant can be present in the coating composition in any amount sufficient to impart the desired visual and/or color effect. The colorant may comprise from 1 to 65 weight percent, such as from 3 to 40 weight percent or 5 to 35 weight percent, with weight percent based on the total weight of the composition.
- For purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers such as those expressing values, amounts, percentages, ranges, subranges and fractions may be read as if prefaced by the word “about,” even if the term does not expressly appear. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Where a closed or open-ended numerical range is described herein, all numbers, values, amounts, percentages, subranges and fractions within or encompassed by the numerical range are to be considered as being specifically included in and belonging to the original disclosure of this application as if these numbers, values, amounts, percentages, subranges and fractions had been explicitly written out in their entirety.
- Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard variation found in their respective testing measurements.
- As used herein, unless indicated otherwise, a plural term can encompass its singular counterpart and vice versa, unless indicated otherwise. For example, although reference is made herein to “a” conversion composition, “a” sealing composition, and “an” oxidizing agent, a combination (i.e., a plurality) of these components can be used. In addition, in this application, the use of “or” means “and/or” unless specifically stated otherwise, even though “and/or” may be explicitly used in certain instances.
- As used herein, “including,” “containing” and like terms are understood in the context of this application to be synonymous with “comprising” and are therefore open-ended and do not exclude the presence of additional undescribed and/or unrecited elements, materials, ingredients and/or method steps. As used herein, “consisting of” is understood in the context of this application to exclude the presence of any unspecified element, ingredient and/or method step. As used herein, “consisting essentially of” is understood in the context of this application to include the specified elements, materials, ingredients and/or method steps “and those that do not materially affect the basic and novel characteristic(s)” of what is being described.
- Unless otherwise disclosed herein, the term “substantially free,” when used with respect to the absence of a particular material, means that such material, if present at all in a composition, a bath containing the composition, and/or layers formed from and comprising the composition, only is present in a trace amount of 5 ppm or less based on a total weight of the composition or layer(s), as the case may be, excluding any amount of such material that may be present or derived as a result of drag-in, substrate(s), and/or dissolution of equipment). Unless otherwise disclosed herein, the term “essentially free,” when used with respect to the absence of a particular material, means that such material, if present at all in a composition, a bath containing the composition, and/or layers formed from and comprising the composition, only is present in a trace amount of 1 ppm or less based on a total weight of the composition or layer(s), as the case may be. Unless otherwise disclosed herein, the term “completely free,” when used with respect to the absence of a particular material, means that such material, if present at all in a composition, a bath containing the composition, and/or layers formed from and comprising the composition, is absent from the composition, the bath containing the composition, and/or layers formed from and comprising same (i.e., the composition, bath containing the composition, and/or layers formed from and comprising the composition contain 0 ppm of such material).
- As used herein, the terms “on,” “onto,” “applied on,” “applied onto,” “formed on,” “deposited on,” “deposited onto,” mean formed, overlaid, deposited, and/or provided on but not necessarily in contact with the surface. For example, a coating layer “formed over” a substrate does not preclude the presence of one or more other intervening coating layers of the same or different composition located between the formed coating layer and the substrate.
- As used herein, a “salt” refers to an ionic compound made up of metal cations and non-metallic anions and having an overall electrical charge of zero. Salts may be hydrated or anhydrous.
- As used herein, “aqueous composition” refers to solution or dispersion in a medium that comprises predominantly water. For example, the aqueous medium may comprise water in an amount of more than 50 wt. %, or more than 70 wt. % or more than 80 wt. % or more than 90 wt. % or more than 95 wt. %, based on the total weight of the medium. The aqueous medium may for example consist substantially of water.
- As used herein, “conversion composition” refers to a composition that is capable of reacting with and chemically altering the substrate surface and binding to it to form a film that affords corrosion protection.
- As used herein, “conversion bath” refers to an aqueous bath containing the conversion composition and that may contain components that are byproducts of the process of contacting a substrate with the conversion composition.
- As used herein, the term “conversion composition metal cation(s)” refers to metal cations of a lanthanide series element, a Group IIA metal, a Group IIIB metal, a Group IVB metal, a Group VB metal, a Group VIB metal, a Group VIIB metal, and/or a Group XII metal.
- As used herein, a “sealing composition” refers to a composition, e.g. a solution or dispersion, that affects a substrate surface or a material deposited onto a substrate surface in such a way as to alter the physical and/or chemical properties of the substrate surface (i.e., the composition affords corrosion protection).
- As used herein, the term “Group IA metal” refers to an element that is in Group IA of the CAS version of the Periodic Table of the Elements as is shown, for example, in the Handbook of Chemistry and Physics, 63rd edition (1983), corresponding to Group 1 in the actual IUPAC numbering.
- As used herein, the term “Group IA metal compound” refers to compounds that include at least one element that is in Group IA of the CAS version of the Periodic Table of the Elements.
- As used herein, the term “Group IIIB metal” refers to yttrium and scandium of the CAS version of the Periodic Table of the Elements as is shown, for example, in the Handbook of Chemistry and Physics, 63rd edition (1983), corresponding to Group 3 in the actual IUPAC numbering. For clarity, “Group IIIB metal” expressly excludes lanthanide series elements.
- As used herein, the term “Group IIIB metal compound” refers to compounds that include at least one element that is in group IIIB of the CAS version of the Periodic Table of the Elements as defined above.
- As used herein, the term “Group IVB metal” refers to an element that is in group IVB of the CAS version of the Periodic Table of the Elements as is shown, for example, in the Handbook of Chemistry and Physics, 63rd edition (1983), corresponding to Group 4 in the actual IUPAC numbering.
- As used herein, the term “Group IVB metal compound” refers to compounds that include at least one element that is in Group IVB of the CAS version of the Periodic Table of the Elements.
- As used herein, the term “Group VB metal” refers to an element that is in group VB of the CAS version of the Periodic Table of the Elements as is shown, for example, in the Handbook of Chemistry and Physics, 63rd edition (1983), corresponding to Group 5 in the actual IUPAC numbering.
- As used herein, the term “Group VB metal compound” refers to compounds that include at least one element that is in Group VB of the CAS version of the Periodic Table of the Elements.
- As used herein, the term “Group VIB metal” refers to an element that is in group VIB of the CAS version of the Periodic Table of the Elements as is shown, for example, in the Handbook of Chemistry and Physics, 63rd edition (1983), corresponding to Group 6 in the actual IUPAC numbering.
- As used herein, the term “Group VIB metal compound” refers to compounds that include at least one element that is in Group VIB of the CAS version of the Periodic Table of the Elements.
- As used herein, the term “lanthanide series elements” refers to elements 57-71 of the CAS version of the Periodic Table of the Elements and includes elemental versions of the lanthanide series elements. In embodiments, the lanthanide series elements may be those which have both common oxidation states of +3 and +4, referred to hereinafter as +3/+4 oxidation states.
- As used herein, the term “lanthanide compound” refers to compounds that include at least one of elements 57-71 of the CAS version of the Periodic Table of the Elements.
- As used herein, the term “halogen” refers to any of the elements fluorine, chlorine, bromine, iodine, and astatine of the CAS version of the Periodic Table of the Elements, corresponding to Group VIIA of the periodic table.
- As used herein, the term “halide” refers to compounds that include at least one halogen.
- As used herein, the term “aluminum,” when used in reference to a substrate, refers to substrates made of or comprising aluminum and/or aluminum alloy, and clad aluminum substrates.
- As used herein, the term “oxidizing agent,” when used with respect to a component of the conversion composition, refers to a chemical which is capable of oxidizing at least one of: a metal present in the substrate which is contacted by the conversion composition, a lanthanide series element present in the conversion composition, and/or a metal-complexing agent present in the conversion composition. As used herein with respect to “oxidizing agent,” the phrase “capable of oxidizing” means capable of removing electrons from an atom or a molecule present in the substrate or the conversion composition, as the case may be, thereby decreasing the number of electrons of such atom or molecule.
- Pitting corrosion is the localized formation of corrosion by which cavities or holes are produced in a substrate. The term “pit,” as used herein, refers to such cavities or holes resulting from pitting corrosion and is characterized by (1) a rounded, elongated or irregular appearance when viewed normal to the test panel surface, (2) a “comet-tail”, a line, or a “halo” (i.e., a surface discoloration) emanating from the pitting cavity, and (3) the presence of corrosion byproduct (e.g., white, grayish or black granular, powdery or amorphous material) inside or immediately around the pit. An observed surface cavity or hole must exhibit at least two of the above characteristics to be considered a corrosion pit. Surface cavities or holes that exhibit only one of these characteristics may require additional analysis before being classified as a corrosion pit. Visual inspection using a microscope with 10× magnification is used to determine the presence of corrosion byproducts when corrosion byproducts are not visible with the unaided eye.
- Unless otherwise disclosed herein, as used herein, the terms “total composition weight”, “total weight of a composition” or similar terms refer to the total weight of all ingredients being present in the respective composition including any carriers and solvents.
- In view of the foregoing description the present invention thus relates in particular, without being limited thereto, to the following Aspects 1-35: ASPECTS
- 1. A method of treating a substrate comprising: contacting at least a portion of the substrate surface with a sealing composition comprising a lithium cation.
- 2. The method of Aspect 1, wherein the sealing composition is applied to provide a layer of the dried sealing composition having a thickness of 5 nm to 550 nm.
- 3. The method of either of the preceding Aspects, wherein the lithium cation is present in the sealing composition as a lithium salt.
- 4. The method of any of the preceding Aspects, wherein the lithium cation is present in the sealing composition in an amount of 5 ppm to 5500 ppm (as lithium cation) based on total weight of the sealing composition.
- 6. The method of any of the preceding Aspects, wherein the sealing composition further comprises a carbonate source, a hydroxide source, or combinations thereof.
- 7. The method of any of the preceding Aspects, wherein the sealing composition further comprises a source of a Group IA metal other than lithium, a Group VB metal source, a Group VIB metal source, a corrosion inhibitor, an indicator compound, or combinations thereof.
- 8. The method of any of the preceding Aspects, wherein the pH of the sealing composition is 9.5 to 12.5.
- 9. The method of any of the preceding Aspects, wherein the sealing composition is substantially free of fluoride, a Group IIA metal cation, a cobalt ion, a vanadium ion, or combinations thereof.
- 10. The method of any of the preceding Aspects, wherein, following the contacting with the sealing composition, the substrate is not rinse with water prior to contacting at least a portion of the substrate surface with subsequent treatment compositions.
- 11. The method of any of the preceding Aspects, wherein the temperature of the sealing composition is 40 F to 160 F.
- 12. The method of any of the preceding Aspects, wherein the contacting with the sealing composition is for 1 second to 15 minutes.
- 13. The method of any of the preceding Aspects further comprising contacting at least a portion of the substrate surface with a conversion composition comprising a lanthanide series element cation, a Group IIIB metal cation, a Group IVB metal cation, or combinations thereof; wherein the contacting with the conversion composition occurs prior to the contacting with the sealing composition.
- 14. The method of Aspect 13, wherein the conversion composition is applied to provide a film on the substrate resulting in a level of the lanthanide series element cation, Group IIIB metal cation, and/or Group IV metal cation on the treated substrate surface of at least 100 counts greater than on a surface of a substrate that does not have the film thereon as measured by X-ray fluorescence (measured using X-Met 7500, Oxford Instruments; operating parameters 60 second timed assay, 15 Kv, 45 μA, filter 3, T(p)=1.51 μs for lanthanides, Group IIIB metals, and Group IVB metals except zirconium; operating parameters 60 second timed assay, 40 Kv, 10 μA, filter 4, T(p)=1.51 μs for zirconium).
- 15. The method of any of Aspects 13 or 14, wherein the lanthanide series element cation, Group IIIB metal cation, and/or Group IVB metal cation comprises cerium, praseodymium, yttrium, zirconium, titanium, or combinations thereof.
- 16. The method of any of Aspects 13 to 15, wherein the cations of the lanthanide series element, Group IIIB metal, and/or Group IVB metal are present in the conversion composition in an amount of 5 ppm to 25,000 ppm based on total weight of the conversion composition.
- 17. The method of any of Aspects 13 to 16, wherein the conversion composition further comprises a halide, a nitrate, or combinations thereof.
- 18. The method of Aspect 17, wherein the halide is present in the conversion composition in an amount of 9 ppm to 20,000 ppm based on total weight of the conversion composition.
- 19. The method of Aspect 17, wherein the nitrate is present in the conversion composition in an amount of 2 ppm to 5000 ppm based on total weight of the conversion composition.
- 20. The method of any of Aspects 13 to 19, wherein the conversion composition further comprises an oxidizing agent.
- 21. The method of Aspect 20, wherein the oxidizing agent is present in the conversion composition in an amount of 500 ppm to 3000 ppm based on total weight of the conversion composition.
- 22. The method of any of Aspects 13 to 21, wherein the pH of the conversion composition is 2.0 to 4.5.
- 23. The method of any of Aspects 13 to 22, further comprising heating the substrate at a temperature of 110 C to 232 C.
- 24. The method of any of the preceding Aspects, wherein the substrate comprises aluminum, aluminum alloys, or combinations thereof.
- 25. The method of any of the preceding Aspects, wherein the substrate comprises an aluminum alloy comprising copper in an amount of 1 percent by weight to 10 percent by weight.
- 26. A system for treated a substrate comprising;
- a conversion composition for treating at least a portion of the substrate, comprising a lanthanide series cation, a Group IIIB metal cation, a Group IVB metal cation, or combinations thereof; and
- a sealing composition for treating at least a portion of the substrate, comprising a lithium cation.
- 27. The system of Aspect 26, wherein the sealing composition has a pH of 9.5 to 12.5.
- 28. The system of Aspect 26 or 27, further comprising an alkaline cleaning composition.
- 29. A substrate obtainable by the method of any of Aspects 1 to 25.
- 30. A substrate obtainable by the system of any of Aspects 26 to 28.
- 31. The substrate of Aspect 29 or 30, wherein at least a portion of the substrate surface is sanded.
- 32. The substrate according to any of Aspects 29 to 31, wherein substrate treated with the sealing composition has at least a 50% reduction in the number of pits on the substrate surface compared to a substrate not treated with the sealing composition following 3 day exposure in neutral salt spray cabinet operated according to ASTM B117.
- 33. The substrate according to any of Aspects 29 to 32, wherein the substrate treated with the conversion composition and the sealing composition has at least a 50% reduction in the number of pits on the substrate surface compared to a substrate treated with the conversion composition or the sealing composition but not the conversion composition and the sealing composition following 7 day exposure in neutral salt spray cabinet operated according to ASTM B117.
- 34. The substrate according to any of Aspects 29 to 33, further comprising a primer layer.
- 35. The substrate according to any of Aspects 29 to 34, further comprising a topcoat layer.
- Whereas particular features of the present invention have been described above for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details of the coating composition, coating, and methods disclosed herein may be made without departing from the scope in the appended claims.
- Illustrating the invention are the following examples that are not to be considered as limiting the invention to their details. All parts and percentages in the examples, as well as throughout the specification, are by weight unless otherwise indicated.
-
-
TABLE 3 Materials for Examples 1-5 Ridoline 2981 Henkel AG & Co. (Germany) Deoxidizer 6-162 (6-16) Henkel AG & Co. Nitric acid cerium nitrate solution ProChem Inc. (Rockford, IL) (65.37% Ce(NO3)3•6H2O) yttrium nitrate solution ProChem Inc. (72.45% Y(NO3)3•6H2O) cerium chloride solution ProChem Inc. (32.2% as CeO2*) hydrogen peroxide (30% H2O2) Alfa Aesar (Ward Hill, MA) sodium hydroxide pellets, 98% Alfa Aesar sodium phosphate dodecahydrate, 97% Alfa Aesar polyvinylpyrrolidone (PVP), 8000 m.w. Alfa Aesar Allantoin3, 98% Alfa Aesar 2,5-dimercapto-1,3,4-thiadiazole, 98% Acros Organics (Geel, Belgium) Carbowet GA1004, 100% Air Products (Cleveland, OH) lithium carbonate, 98% Alfa Aesar sodium vanadium oxide, 96% Ward Hill sodium molybdenum oxide dehydrate, Alfa Aesar 98% 1A non-silicated cleaner. 2A deoxidizer. 3(2,5-dioxo-4-imidazolidinyl) urea. 4A non-ionic surfactant. *As per the supplier's analytical report, the concentration of cerium in the cerium chloride solution is measured as cerium oxide (CeO2). -
TABLE 4 Equipment Technique Equipment Operating parameters X-ray X-Met 7500, Operating Parameters for lanthanides, Fluorescence Oxford Group IIIB metals and Group IVB metals (XRF) Instruments except zirconium: Measurements 60 second timed assay Voltage/current/filter: 15Kv_45μA_filter 3 Dpp parameters: T(p) = 1.5 μs -
TABLE 5A Example A INGREDIENTS % BY WEIGHT sodium hydroxide pellets, 98% 1.6 sodium phosphate dodecahydrate, 97% 6.3 polyvinylpyrrolidone (PVP), 8000 m.w. 0.02 Allantoin, 98% 0.03 2,5-dimercapto-1,3,4-thiadiazole(DMTD), 98% 1.00 Carbowet GA100 4.1 deionized water 98.7 - The ingredients used to prepare a solution of cleaner Example A are provided in Table 5A. Sodium hydroxide and sodium phosphate were completely dissolved in deionized water under mild mechanical agitation using a stir plate (VWR, 7×7 CER HOT/STIR). Next, the PVP was stirred in until dissolved, and then Allantoin was added and stirred until dissolved, and then the DMTD was added and stirred until dissolved. After the DMTD was completely dissolved, Carbowet GA100 was stirred in under mild mechanical agitation as above.
-
TABLE 5B Example B Ridoline 298 (R298), parts by volume 100 tap water, parts by volume 900 - The solution of Example B was prepared using the ingredients shown in Table 5B, per manufacturer's instructions.
-
TABLE 6 Deoxidizer for Examples 4 and 5 Material Example C Deoxidizer 6-16, parts by volume 100 nitric acid, parts by volume 200 tap water, parts by volume 1700 - Deoxidizer solutions of Example C was prepared using the ingredients shown in Table 6, per manufacturers' instructions.
-
TABLE 7 Conversion Coating Compositions for Examples 1 and 3-8 Yttrium Cerium Cerium Hydrogen Nitrate Nitrate Chloride Peroxide Deionized Solution Solution Solution Solution Water (g) (g) (g) (g) (g) Example E 12.48 10.40 0.04 1.04 1953 Example F 0.00 0.00 84.0 5.20 1953 - The ingredients used to prepare conversion coating compositions E and F are shown in Table 7.
- For the conversion coating composition of Example E, the cerium nitrate, yttrium nitrate and cerium chloride solutions were weighted into individual cups. Then using 500 grams of deionized water, the solutions were transferred to a vessel containing 1000 grams of deionized water under mild agitation. The remaining 453 grams of water was added and the solution was stirred for 10 minutes to ensure uniformity before the hydrogen peroxide was added. The final solution stirred for a minimum of 30 minutes before use.
- For the conversion coating composition of Example F, solutions were prepared by adding the cerium chloride solution to the full amount of deionized water under mild agitation. The solution was stirred for 10 minutes to ensure uniformity before the hydrogen peroxide was added. The final solution stirred for a minimum of 30 minutes before use.
-
TABLE 8 Sealing Compositions of Examples 2-9 Material Example G Example H Example I lithium carbonate, grams 3.07 3.07 3.07 deionized water, grams 1996.93 1996.93 1996.93 sodium vanadium oxide, grams — 1.67 — sodium molybdenum oxide — — 1.67 dehydrate, grams - The sealing solution of Example G was prepared using the ingredients shown in Table 8 by dissolving lithium carbonate in deionized water under mild agitation using the stir plate as described above.
- The sealing solution of Example H was prepared using the ingredients shown in Table 8 by dissolving lithium carbonate in deionized water under mild agitation using the stir plate as described above. Next, the sodium vanadium oxide was added and dissolved under mild agitation as described above.
- The sealing solution of Example I was prepared using the ingredients shown in Table 8 by dissolving lithium carbonate in deionized water under mild agitation using the stir plate as described above. Next, the sodium molybdenum oxide dehydrate was added and dissolved under mild agitation as described above.
- Aluminum 2024T3 bare substrate (Priority Metals, Orange County, Calif.) measuring 3″×5″×0.032″ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning. The panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation. The panel was then immersed in two subsequent deionized water rinses for two minutes each, both at ambient temperature with intermittent agitation. After the second rinse, the panel received a cascading deionized water rinse for 10 seconds. The panel was then immersed in the conversion coating composition of Example E for 5 minutes at ambient temperature and without agitation. After the conversion coating, the panel received an immersion rinse in deionized water for 1 minute at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse. The panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3″×5″×0.032″ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning. The panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation. The panel was then immersed in two subsequent deionized water rinses for two minutes each, both at ambient temperature with intermittent agitation. After the second rinse, the panel received a cascading deionized water rinse for 10 seconds. The panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation. The panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3″×5″×0.032″ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning. The panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation. The panel was then immersed in two subsequent deionized water rinses for two minutes each, both at ambient temperature with intermittent agitation. After the second rinse, the panel received a cascading deionized water rinse for 10 seconds. The panel was then immersed in the conversion coating composition of Example E for 5 minutes at ambient temperature and without agitation. After the conversion coating, the panel received an immersion rinse in deionized water for 1 minute at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse. The panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation. The panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3″×5″×0.032″ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning. The panel was immersed in the cleaner solution of Example B for 2 minutes at 55° C. with mild agitation. The panel was then immersed in a tap water rinse for one minute at ambient temperature with mild agitation followed by a 10 second cascading tap water rinse. The panel was immersed in a deoxidizing solution of Example C for 1.5 minutes at ambient temperature followed by a one minute immersion rinse in tap water at ambient temperature and mild agitation followed by a 10 second cascading rinse. The panel was then immersed in the conversion coating composition of Example E for 5 minutes at ambient temperature and without agitation. After the conversion coating, the panel received an immersion rinse in deionized water for 1 minute at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse. The panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation. The panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3″×5″×0.032″ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning. The panel was immersed in the cleaner solution of Example B for 2 minutes at 55° C. with mild agitation. The panel was then immersed in a tap water rinse for one minute at ambient temperature with mild agitation followed by a 10 second cascading tap water rinse. The panel was immersed in a deoxidizing solution of Example C for 1.5 minutes at ambient temperature followed by a one minute immersion rinse in tap water at ambient temperature and mild agitation followed by a 10 second cascading rinse. The panel was then immersed in the conversion coating composition of Example F for 7 minutes at ambient temperature and without agitation. After the conversion coating, the panel received an immersion rinse in deionized water for 1 minute at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse. The panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation. The panel was air dried at ambient conditions overnight before testing.
- A 3′×10″×0.032″ panel of Al 2024-T3 was solvent wiped on both sides with Methyl Ethyl Ketone using a lint-free paper towel until the surface was visually free from grease and oil. The panel was then immersed in the cleaner solution of Example A for 7 minutes at ambient temperature. Next, the panel was then rinsed using a de-ionized water spray rinse for two minutes followed by a de-ionized water immersion rinse for two minutes. The panel was then immersed in the conversion coating composition of Example E for 5 minutes at ambient temperature. The panel was then immersed in de-ionized water for two minutes, followed by a second de-ionized water rinse for two minutes. The metal substrate was then immersed in the sealing composition of Example G for two minutes. The panel was allowed to air dry at ambient conditions prior to testing.
- A 3″×10″×0.032″ panel of Al 2024-T3 was solvent wiped on both sides with Methyl Ethyl Ketone using a lint-free paper towel until the surface was visually free from grease and oil. The panel was then immersed in the cleaner solution of Example A for 7 minutes at ambient temperature. Next, the panel was then rinsed using a de-ionized water spray rinse for two minutes followed by a de-ionized water immersion rinse for two minutes. The panel was then immersed in the conversion coating composition of Example E for 5 minutes at ambient temperature. The panel was then immersed in de-ionized water for two minutes, followed by a second de-ionized water rinse for two minutes. The metal substrate was then immersed in the sealing composition of Example H for 2 minutes. The panel was allowed to air dry at ambient conditions prior to testing.
- A 3″×10″×0.032″ panel of Al 2024-T3 was solvent wiped on both sides with Methyl Ethyl Ketone using a lint-free paper towel until the surface was visually free from grease and oil. The panel was then immersed in the cleaner solution of Example A for 7 minutes. Next, the panel was rinsed using a de-ionized water spray rinse for two minutes followed by a de-ionized water immersion rinse for two minutes. The panel was then immersed in the conversion coating composition of Example E for 5 minutes at ambient temperature. The panel was then immersed in de-ionized water for two minutes, followed by a second de-ionized water rinse for two minutes. The metal substrate was then immersed in the sealing composition of Example I described above for 2 minutes. The panel was allowed to air dry at ambient conditions prior to testing.
- The panels from Examples 1-5 were analyzed for deposition of lanthanide using X-ray fluorescence (measured using X-Met 7500, Oxford Instruments; operating parameters 60 second timed assay, 15 Kv, 45 μA, filter 3, T(p)=1.5 μs). Data are reported in Table 9.
- The panels from Examples 1-5 were evaluated for corrosion resistance by placing each panel in a 7 day exposure neutral salt spray cabinet operated according to ASTM B117. Corrosion performance was evaluated by counting the number of pits visible to the naked eye on the panels. Data are reported in Table 9.
- The panels from Examples 6-8 were evaluated for corrosion resistance by placing each panels in a 3 day exposure neutral salt spray cabinet operated according to ASTM B117. Corrosion performance was evaluated using the rating scale shown in Table 10. Data are reported in Table 9.
-
TABLE 9 Corrosion performance and XRF readings Conversion Sealing Clean/Deox Composition Composition Salt Spray XRF Reading 7 days 1 Example A Example E None 100+ pits 662 (Ce) 2 Example A None Example G 100+ pits 299 (Ce) - baseline 3 Example A Example E Example G 0 pits 768 (Ce) 4 Example B/C Example E Example G 100+ pits 313 (Ce) 5 Example B/C Example F Example G 3 pits 1478 (Ce) 3 days 6 Example A Example E Example G 8 (rating) n/a 7 Example A Example E Example H 9 (rating) n/a 8 Example A Example E Example I 10 (rating) n/a -
TABLE 10 Rating Scale for Salt Spray Rating Description 10 identical to how they went in to test/no corrosion 9 passes with no “countable” pits (if there is a pit, it's either from an edge, scratch, pre-existing, etc.) 8 ≤five pits with corrosion salt tails 7 ≥5 pits with tails and ≤15 pits total 6 >15 pits total and ≤40 pits total 5 30% surface corrosion 4 50% surface corrosion 3 70% surface corrosion 2 85% surface corrosion 1 100% surface corrosion - The data shown in Table 9 demonstrate that the combination contacting a substrate surface with a lanthanide-containing conversion composition and a lithium-containing sealing composition that includes either a molybdenum salt or a vanadium salt further reduced the level of pitting on the substrate surface following 3 day exposure in neutral salt spray cabinet operated according to ASTM B117 compared to a substrate surface that has been contacted with the conversion composition and a sealing composition that does not include the molybdenum salt or the vanadium salt.
- The data shown in Table 9 also demonstrate that contacting an anodized substrate with the lithium-containing sealing composition resulted in a treated substrate which had a salt spray rating of 8 following 7 day exposure in neutral salt spray cabinet operated according to ASTM B117.
- The data shown in Table 9 also demonstrate that the combination of a film formed from a lanthanide-containing conversion composition with a layer formed from a lithium-containing sealing composition results in at least a 50% reduction in the number of pits on the substrate surface compared to a substrate surface that has the conversion composition film or the sealing composition layer but not both following 7 day exposure in neutral salt spray cabinet operated according to ASTM B117.
-
-
TABLE 11 Additional Materials for Examples BB, FF and II through LL Yttrium Chloride, 99.9% Alfa Aesar Potassium Hexafluorozirconate, 99% Alfa Aesar Potassium Hexafluorotitanate, 97% Alfa Aesar -
TABLE 12 Additional Conversion Coating Compositions for Examples BB through FF Yttrium Yttrium Cerium Cerium Hydrogen Nitrate Chloride Nitrate Chloride Peroxide Deionized Solution (g) Solid (g) Solution (g) Solution (g) Solution (g) Water (g) Example J — — 25.08 .04 1.01 1874.88 Example K 19.97 0.015 — — 1.01 1880.03 -
TABLE 13 Additional Conversion Coating Compositions for Examples JJ through MM Potassium Potassium Hydrogen Hexafluoro- Hexafluoro- Peroxide Deionized zirconate titanate Solution Water (g) (g) (g) (g) Example L 2.38 — 1.19 1897.60 Example M — 2.38 1.00 1897.60 - The ingredients used to prepare conversion coating compositions J and K are shown in Table 12.
- For the conversion coating composition of Example J, the cerium nitrate and cerium chloride solutions were weighted into individual cups. Then using 500 grams of deionized water, the solutions were transferred to a vessel containing 1000 grams of deionized water under mild agitation. The remaining 374.88 grams of water were added and the solution was stirred for 10 minutes to ensure uniformity before the hydrogen peroxide was added. The final solution stirred for a minimum of 30 minutes before use.
- For the conversion coating composition of Example K, the yttrium nitrate and yttrium chloride solutions were weighted into individual cups. Then using 500 grams of deionized water, the solutions were transferred to a vessel containing 1000 grams of deionized water under mild agitation. The remaining 380.03 grams of water were added and the solution was stirred for 10 minutes to ensure uniformity before the hydrogen peroxide was added. The final solution stirred for a minimum of 30 minutes before use.
- For the conversion coating compositions of Examples II through LL, the entire amount of deionized water was weighed into a container. The zirconium salt was measured into a separate cup then transferred into the vessel containing the deionized water while under moderate stirring. The solution continued to stir for 15 minutes to allow the entire amount of salt to dissolve. This exact process was used to prepare the titanium solution.
- Aluminum 2024T3 bare substrate (Priority Metals, Orange County, Calif.) measuring 3″×5″×0.032″ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning. The panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation. The panel was then immersed in two subsequent deionized water rinses for two minutes each, both at ambient temperature with intermittent agitation. After the second rinse, the panel was air dried at ambient conditions overnight before testing.
- The panel was placed in 3 day and 7 day exposure in neutral salt spray cabinet operated according to ASTM B117. Corrosion performance was evaluated by counting the number of pits visible to the naked eye on the panels. Data are reported in Table 14.
- Aluminum 2024T3 bare substrate (Priority Metals, Orange County, Calif.) measuring 3″×5″×0.032″ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning. The panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation. The panel was then immersed in two subsequent deionized water rinses for two minutes each, both at ambient temperature with intermittent agitation. After the second rinse, the panel received a cascading deionized water rinse for 10 seconds. The panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation. The panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate (Priority Metals, Orange County, Calif.) measuring 3″×5″×0.032″ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning. The panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation. The panel was then immersed in two subsequent deionized water rinses for two minutes each, both at ambient temperature with intermittent agitation. After the second rinse, the panel received a cascading deionized water rinse for 10 seconds. The panel was then immersed in the conversion coating of Example J for 5 minutes at ambient temperature and without agitation. After the conversion coating, the panel received an immersion rinse in deionized water for 2 minutes at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse. The panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate (Priority Metals, Orange County, Calif.) measuring 3″×5″×0.032″ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning. The panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation. The panel was then immersed in two subsequent deionized water rinses for two minutes each, both at ambient temperature with intermittent agitation. After the second rinse, the panel received a cascading deionized water rinse for 10 seconds. The panel was then immersed in the conversion coating of Example K for 5 minutes at ambient temperature and without agitation. After the conversion coating, the panel received an immersion rinse in deionized water for 2 minutes at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse. The panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3″×5″×0.032″ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning. The panel was immersed in the cleaner solution of Example B for 2 minutes at 55° C. with mild agitation. The panel was then immersed in a tap water rinse for one minute at ambient temperature with mild agitation followed by a 10 second cascading tap water rinse. The panel was immersed in a deoxidizing solution of Example C for 1.5 minutes at ambient temperature followed by a one minute immersion rinse in tap water at ambient temperature and mild agitation followed by a 10 second cascading rinse. The panel was then immersed in the conversion coating of Example J for 5 minutes at ambient temperature and without agitation. After the conversion coating, the panel received an immersion rinse in deionized water for 2 minutes at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse. The panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation. The panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3″×5″×0.032″ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning. The panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation. The panel was then immersed in two subsequent deionized water rinses for two minutes each, both at ambient temperature with intermittent agitation. After the second rinse, the panel received a cascading deionized water rinse for 10 seconds. The panel was then immersed in the conversion coating of Example J for 5 minutes at ambient temperature and without agitation. After the conversion coating, the panel received an immersion rinse in deionized water for 2 minutes at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse. The panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation. The panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3″×5″×0.032″ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning. The panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation. The panel was then immersed in two subsequent deionized water rinses for two minutes each, both at ambient temperature with intermittent agitation. After the second rinse, the panel received a cascading deionized water rinse for 10 seconds. The panel was then immersed in the conversion coating of Example K for 5 minutes at ambient temperature and without agitation. After the conversion coating, the panel received an immersion rinse in deionized water for 2 minutes at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse. The panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation. The panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3″×5″×0.032″ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning. The panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation. The panel was then immersed in two subsequent deionized water rinses for two minutes each, both at ambient temperature with intermittent agitation. After the second rinse, the panel received a cascading deionized water rinse for 10 seconds. The panel was then immersed in the conversion coating of Example E for 5 minutes at ambient temperature and without agitation. After the conversion coating, the panel received an immersion rinse in deionized water for 2 minutes at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse. The panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation. The panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3″×5″×0.032″ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning. The panel was immersed in the cleaner solution of Example B for 2 minutes at 55° C. with mild agitation. The panel was then immersed in a tap water rinse for one minute at ambient temperature with mild agitation followed by a 10 second cascading tap water rinse. The panel was immersed in a deoxidizing solution of Example C for 1.5 minutes at ambient temperature followed by a one minute immersion rinse in tap water at ambient temperature and mild agitation followed by a 10 second cascading rinse. The panel was then immersed in the conversion coating of Example F for 5 minutes at ambient temperature and without agitation. After the conversion coating, the panel received an immersion rinse in deionized water for 2 minutes at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse. The panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation. The panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3″×5″×0.032″ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning. The panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation. The panel was then immersed in an ambient deionized water rinse for 5 seconds followed by an ambient deionized water immersion rinse for 2 minutes with intermittent agitation. After the second rinse, the panel received a cascading deionized water rinse for 10 seconds. The panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation. The panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3″×5″×0.032″ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning. The panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation. The panel was then immersed in an ambient deionized water rinse for 5 seconds followed by an ambient deionized water immersion rinse for 2 minutes with intermittent agitation. After the second rinse, the panel received a cascading deionized water rinse for 10 seconds. The panel was then immersed in the conversion coating of Example L for 1 minute at ambient temperature and without agitation. After the conversion coating, the panel received an immersion rinse in deionized water for 2 minutes at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse. The panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3″×5″×0.032″ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning. The panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation. The panel was then immersed in an ambient deionized water rinse for 5 seconds followed by an ambient deionized water immersion rinse for 2 minutes with intermittent agitation. After the second rinse, the panel received a cascading deionized water rinse for 10 seconds. The panel was then immersed in the conversion coating of Example L for 1 minute at ambient temperature and without agitation. After the conversion coating, the panel received an immersion rinse in deionized water for 2 minutes at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse. The panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation. The panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3″×5″×0.032″ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning. The panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation. The panel was then immersed in an ambient deionized water rinse for 5 seconds followed by an ambient deionized water immersion rinse for 2 minutes with intermittent agitation. After the second rinse, the panel received a cascading deionized water rinse for 10 seconds. The panel was then immersed in the conversion coating of Example M for 1 minute at ambient temperature and without agitation. After the conversion coating, the panel received an immersion rinse in deionized water for 2 minutes at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse. The panel was air dried at ambient conditions overnight before testing.
- Aluminum 2024T3 bare substrate measuring 3″×5″×0.032″ was hand-wiped with methyl ethyl ketone (100%) and a disposable cloth and allowed to air dry prior to chemical cleaning. The panel was immersed in the cleaner solution of Example A for 3.5 minutes at ambient temperature with intermittent agitation. The panel was then immersed in an ambient deionized water rinse for 5 seconds followed by an ambient deionized water immersion rinse for 2 minutes with intermittent agitation. After the second rinse, the panel received a cascading deionized water rinse for 10 seconds. The panel was then immersed in the conversion coating of Example M for 1 minute at ambient temperature and without agitation. After the conversion coating, the panel received an immersion rinse in deionized water for 2 minutes at ambient temperature with intermittent agitation followed by a 10 second cascading deionized water rinse. The panel was then immersed in the seal solution of Example G for 2 minutes at ambient temperature with intermittent agitation. The panel was air dried at ambient conditions overnight before testing.
- The panels of Examples AA through MM were analyzed for deposition of lanthanide using X-ray fluorescence (measured using X-Met 7500, Oxford Instruments; operating parameters 60 second timed assay, 15 Kv, 45 μA, filter 3, T(p)=1.5 μs). Data are reported in Table 14.
- For each of Examples AA through MM, one panel was placed in a 3 day exposure and one panel was placed in a 7 day exposure in a neutral salt spray cabinet operated according to ASTM B117. Corrosion performance was evaluated by counting the number of pits visible to the naked eye on the panels. Data are reported in Table 14.
-
TABLE 4 Corrosion performance and XRF readings (Example AAA and AA-MM) Conversion Sealing Salt Spray XRF Reading Clean/Deox Composition Composition (No of Pits) Ce Y Zr Ti 7 days AAA Example A none none 100+ 436 322 — — (baseline) (baseline) AA Example A none Example G 79 454 345 — — BB Example A Example J none 100+ 850 — — — CC Example A Example K none 100+ — 418 — — DD Example B/C Example J Example G 59 444 — — — EE Example A Example J Example G 8 837 — — — FF Example A Example K Example G 53 — 429 — — GG Example A Example E Example G 7 845 — — — HH Example B/C Example F Example G 36 909 — — — Example A none none — — — 630 331 (baseline) (baseline) II Example A none Example G 100+ — — 575 331 JJ Example A Example L none 100+ — — 670 — KK Example A Example L Example G 20 — — 697 — LL Example A Example M none 100+ — — — 607 MM Example A Example M Example G 24 — — — 904 3 days AA Example A none Example G 58 850 — — — BB Example A Example J none 100+ — 418 — — CC Example A Example K none 100+ 444 — — — DD Example B/C Example J Example G 19 837 — — — EE Example A Example J Example G 0 — 429 — — FF Example A Example K Example G 20 845 — — — GG Example A Example E Example G 0 909 — — — HH Example B/C Example F Example G 4 — — 575 331 II Example A None Example G 100+ — — 670 — JJ Example A Example L None 100+ — — 697 — KK Example A Example L Example G 9 — — — 607 LL Example A Example M None 100+ — — — 904 MM Example A Example M Example G 15 - The data in Table 14 above demonstrate that, when compared to a metal substrate that was not treated in accordance with the method of the present invention (Example AAA), a metal substrate that was treated with the sealing composition via the method of the present invention (Example AA) provided a reduction in the amount of corrosion on the treated substrate after exposure to neutral salt spray for 7 days. Evidence of the reduced corrosion is demonstrated by the occurrence of only 79 pits for Example AA versus 100+ pits for Example AAA.
- In Example DD, wherein the substrate was first contacted with a conversion coating comprising a lanthanide series element (cerium) and subsequently contacted with a sealing solution comprising a lithium salt, demonstrated a reduced number of corrosion pits after both 3 days and 7 days exposure to neutral salt spray in comparison to both Examples AA (substrate only contacted with the sealing solution) and BB (substrate only contacted with the lanthanide containing conversion coating).
- In Example EE, wherein the substrate was first contacted with a conversion coating comprising a lanthanide series element (cerium) and subsequently contacted with a sealing solution comprising a lithium salt, demonstrated greater than a 50% reduction in the number of corrosion pits after both 3 days and 7 days exposure to neutral salt spray in comparison to both Examples AA (substrate only contacted with the sealing solution) and BB (substrate only contacted with the lanthanide containing conversion coating). Additionally, the number of pits were further reduced relative to Example DD and the detectable level of cerium on the substrate was measurably greater than that measured for Example DD.
- Example FF, wherein the substrate was first contacted with a conversion coating comprising a lanthanide series element (yttrium) and subsequently contacted with a sealing solution comprising a lithium salt, demonstrated greater than a 50% reduction in the number of corrosion pits after both 3 days and 7 days exposure to neutral salt spray in comparison to both Examples AA (substrate only contacted with the sealing solution) and CC (substrate only contacted with the lanthanide containing conversion coating).
- Example GG, wherein the substrate was first contacted with a conversion coating comprising a lanthanide series element (both cerium and yttrium) and subsequently contacted with a sealing solution comprising a lithium salt, demonstrated a reduced number of corrosion pits after 7 days exposure to neutral salt spray in comparison to both Example AA (substrate only contacted with the sealing solution) and Example 1 (substrate only contacted with the lanthanide containing conversion coating).
- Example HH, wherein the substrate was first contacted with a conversion coating comprising a lanthanide series element (cerium) and subsequently contacted with a sealing solution comprising a lithium salt, demonstrated a reduced number of corrosion pits after 7 days exposure to neutral salt spray in comparison to both Example AA (substrate only contacted with the sealing solution) and Example 4 (substrate only contacted with the lanthanide containing conversion coating). Additionally, the number of pits were further reduced relative to Example DD and the detectable level of cerium on the substrate was measurably greater than that measured for Example DD.
- Example KK, wherein the substrate was first contacted with a conversion coating comprising a Group IVB series element (zirconium) and subsequently contacted with a sealing solution comprising a lithium salt, demonstrated a reduced number of corrosion pits after 7 days exposure to neutral salt spray in comparison to both Examples II (substrate only contacted with the sealing solution) and JJ (substrate only contacted with the Group IVB containing conversion coating).
- Example MM, wherein the substrate was first contacted with a conversion coating comprising a Group IVB series element (titanium) and subsequently contacted with a sealing solution comprising a lithium salt, demonstrated a reduced number of corrosion pits after 7 days exposure to neutral salt spray in comparison to both Examples II (substrate only contacted with the sealing solution) and LL (substrate only contacted with the Group IVB containing conversion coating).
- Aluminum 6111 panels (from ACT Test Panels, LLC) were cut to 4″×6″ sample size. The bottom 3″ of the panels were sanded with P320 grit silicon carbide paper (available from 3M) on a 6″ random orbital palm sander (Advanced Tool Design Model-ATD-2088). Half-sanding the panel surface served to determine any corrosion performance difference between as-milled (unsanded) and sanded substrates. Surface sanding or abrasion is conducted in the field to promote adhesion of subsequent paint applications.
- Each of the half-sanded 6111 aluminum panels were spray cleaned with standard Chemkleen 2010LP/181ALP bath (composed of 1.25 vol. % of Chemkleen 2010LP (a phosphate-free alkaline cleaner available from PPG) and 0.125 vol. % of Chemkleen 181 ALP (a phosphate-free blended surfactant additive, available from PPG) in deionized water) in a stainless steel spray tank using vee-jet nozzles at 10 to 15 psi, for two minutes at 120° F. This was followed by immersion rinse in DI water for 15 seconds, and final spray rinse with DI water for 15 seconds.
- Immediately after spray rinsing, the cleaned panels were introduced into the conversion baths.
- The first set of panels were pretreated with Zircobond 1.5, a zirconium-conversion commercially available from PPG Industries, Inc. A 5-gallon bath was prepared as per manufacturer's instruction to yield a pH of 4.72, a zirconium concentration of 200 ppm, and a free fluoride concentration of 101 ppm. The panels were pretreated by immersion into the conversion bath at 80° F. with low agitation, for 2 minutes. The panels were spray rinsed with DI water for 20 to 30 seconds, and air dried using a Hi-Velocity handheld blow-dryer made by Oster® (model number 078302-300-000) on high-setting at a temperature of about 50-55° C. until fully dry (about 3 to 5 minutes).
- The second set of panels were pretreated with a lithium hydroxide conversion composition. The lithium hydroxide conversion composition was composed of 0.15 wt. % of lithium carbonate (available from Acros Organics) in deionized water. The panels were pretreated by immersion into a 3-gallon bath at ambient temperature for 1 minute, without agitation. Immediately after conversion, the panels were air dried using a Hi-Velocity handheld blow-dryer made by Oster® (model number 078302-300-000) on high-setting at a temperature of about 50-55° C. until fully dry (about 3 to 5 minutes).
- The third set of panels were pretreated with a lithium carbonate conversion composition. The lithium carbonate conversion composition was composed of 0.15 wt. % of lithium carbonate (available from Acros Organics) in deionized water. The panels were pretreated by immersion into a 3-gallon bath at ambient temperature for 1 minute, without agitation. Immediately after conversion, the panels were air dried using a Hi-Velocity handheld blow-dryer made by Oster® (model number 078302-300-000) on high-setting at a temperature of about 50-55° C. until fully dry (about 3 to 5 minutes).
- The pretreated panels were electrocoated with cationic ED6280Z paint (available from PPG) using rectifier (Xantrex Model XFR600-2). A coating dry film thickness of 0.8 mil was achieved by passing a 24.5 C, 21.5 C, and 21.0 C charge for the zirconium, lithium hydroxide, and lithium carbonate conversioned panels, respectively, at a current limit of 0.5 A, and an applied electrical potential of 220 V after a 30 second ramp time using a direct current rectifier (Xantrex Model XFR600-2). The ED6280Z paint bath was maintained at 90° F., with a stir rate of 340 rpm. The electrocoated panels were spray rinsed with DI water. The panels were baked in an electric oven (Despatch Model LFD-1-42) at 177° C. for 25 minutes. The coating thickness was measured using a Permascope (Fischer Technology Inc. Model FMP40C).
- Two corrosion test methods were utilized to evaluate the corrosion performance of the panels: ASTM G85 A2 Cyclic Acidified Salt Fog Testing for 3 weeks, and a filiform corrosion testing for 6 weeks. For the latter test, the panels were placed horizontally in a dessicator containing a thin layer of 12 N hydrochloric acid (HCl) for 1 hr at ambient temperature, such that only the HCl fumes shall come in contact with the sample. Within 5 mins, the panels were placed in a vertical orientation in a humidity cabinet maintained at 40° C. and 80% relative humidity for 6 weeks. Duplicate panels were included for each testing. Prior to corrosion testing, the panels were scribed with an X-configuration. The scribe was positioned with the top legs on the as-milled surface and the bottom legs on the sanded surface. Each leg was 40 mm long.
- Corrosion damage was measured as the perpendicular distance from the scribe to tip of the filament or blister. Each panel provided two sets of five measurements: a set from the top legs for the as-milled surface, and another set from the bottom legs for the sanded surface. Measurements were taken from the five longest corrosion sites. The average corrosion damage was calculated based on a total often measurements from duplicate panels. All readings were measured using a Fowler Sylvac digital caliper Model S 235.
- The average corrosion damage is tabulated in Table 15. Relative to the control Zirconium conversion, both lithium hydroxide and lithium carbonate conversions displayed better corrosion performance on sanded 6111 aluminum alloys. Lithium hydroxide also exhibited superior corrosion performance on the as-milled surface.
-
TABLE 15 Average corrosion damage (Example NN) Average Corrosion Damage (mm) As-milled (unsanded) Sanded Test Zirconium Lithium Lithium Zirconium Lithium Lithium Method (control) Hydroxide Carbonate (control) Hydroxide Carbonate Filiform 4.93 1.74 4.24 12.53 5.30 4.49 Corrosion Test ASTM 2.76 1.92 5.57 10.39 5.01 5.20 G85 A2
Claims (23)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US16/325,010 US20190316261A1 (en) | 2016-08-12 | 2017-08-14 | Sealing Composition |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201662374188P | 2016-08-12 | 2016-08-12 | |
US201662374199P | 2016-08-12 | 2016-08-12 | |
PCT/US2017/046730 WO2018031992A1 (en) | 2016-08-12 | 2017-08-14 | Sealing composition |
US16/325,010 US20190316261A1 (en) | 2016-08-12 | 2017-08-14 | Sealing Composition |
Publications (1)
Publication Number | Publication Date |
---|---|
US20190316261A1 true US20190316261A1 (en) | 2019-10-17 |
Family
ID=59677448
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/325,071 Pending US20210292907A1 (en) | 2016-08-12 | 2017-08-14 | Pretreatment Composition |
US16/325,010 Pending US20190316261A1 (en) | 2016-08-12 | 2017-08-14 | Sealing Composition |
US16/639,327 Active 2039-02-28 US11725286B2 (en) | 2016-08-12 | 2018-02-09 | Two-step pretreatment system and method |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/325,071 Pending US20210292907A1 (en) | 2016-08-12 | 2017-08-14 | Pretreatment Composition |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/639,327 Active 2039-02-28 US11725286B2 (en) | 2016-08-12 | 2018-02-09 | Two-step pretreatment system and method |
Country Status (8)
Country | Link |
---|---|
US (3) | US20210292907A1 (en) |
EP (4) | EP3497263A1 (en) |
KR (6) | KR102450429B1 (en) |
CN (4) | CN113621955A (en) |
CA (3) | CA3032156A1 (en) |
MX (3) | MX2019001708A (en) |
RU (3) | RU2751038C2 (en) |
WO (3) | WO2018031992A1 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2021513007A (en) * | 2018-02-09 | 2021-05-20 | ピーピージー・インダストリーズ・オハイオ・インコーポレイテッドPPG Industries Ohio,Inc. | System for processing metal substrates |
EP3924535A1 (en) * | 2019-02-11 | 2021-12-22 | PPG Industries Ohio Inc. | Systems for treating a metal substrate |
MX2021009972A (en) * | 2019-03-01 | 2021-09-21 | Howmet Aerospace Inc | Metallic substrate treatment methods and articles comprising a phosphonate functionalized layer. |
WO2022055472A1 (en) * | 2020-09-08 | 2022-03-17 | Hewlett-Packard Development Company, L.P. | Housings for electronic devices |
WO2022272015A1 (en) * | 2021-06-24 | 2022-12-29 | Prc-Desoto International, Inc. | Systems and methods for coating multi-layered coated metal substrates |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6206982B1 (en) * | 1994-11-11 | 2001-03-27 | Commonwealth Scientific And Industrial Research Organisation | Process and solution for providing a conversion coating on a metal surface |
WO2014186286A1 (en) * | 2013-05-14 | 2014-11-20 | Prc-Desoto International, Inc. | Permanganate based conversion coating compositions |
Family Cites Families (49)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3912548A (en) | 1973-07-13 | 1975-10-14 | Amchem Prod | Method for treating metal surfaces with compositions comprising zirconium and a polymer |
US4828615A (en) | 1986-01-27 | 1989-05-09 | Chemfil Corporation | Process and composition for sealing a conversion coated surface with a solution containing vanadium |
US5266356A (en) | 1991-06-21 | 1993-11-30 | The Center For Innovative Technology | Method for increasing the corrosion resistance of aluminum and aluminum alloys |
US5306526A (en) * | 1992-04-02 | 1994-04-26 | Ppg Industries, Inc. | Method of treating nonferrous metal surfaces by means of an acid activating agent and an organophosphate or organophosphonate and substrates treated by such method |
JPH05287589A (en) * | 1992-04-03 | 1993-11-02 | Nippon Paint Co Ltd | Formation of chemical coating film of aluminum or its alloy and fluorine-free phosphate chemical treating agent |
CA2087352A1 (en) | 1992-07-01 | 1994-01-02 | David W. Reichgott | Method and composition for treatment of galvanized steel |
US5328525A (en) | 1993-01-05 | 1994-07-12 | Betz Laboratories, Inc. | Method and composition for treatment of metals |
US5449415A (en) | 1993-07-30 | 1995-09-12 | Henkel Corporation | Composition and process for treating metals |
US5411607A (en) | 1993-11-10 | 1995-05-02 | Novamax Technologies Holdings, Inc. | Process and composition for sealing anodized aluminum surfaces |
JP3315529B2 (en) | 1994-06-03 | 2002-08-19 | 日本パーカライジング株式会社 | Composition for surface treatment of aluminum-containing metal material and surface treatment method |
DE19524828A1 (en) | 1995-07-07 | 1997-01-09 | Henkel Kgaa | Process for the heavy metal free compression of anodized metals with solutions containing lithium and fluoride |
US5662746A (en) | 1996-02-23 | 1997-09-02 | Brent America, Inc. | Composition and method for treatment of phosphated metal surfaces |
US5756218A (en) * | 1997-01-09 | 1998-05-26 | Sandia Corporation | Corrosion protective coating for metallic materials |
DE19705701A1 (en) * | 1997-02-14 | 1998-08-20 | Henkel Kgaa | Phosphating metal surfaces for subsequent lacquering |
ZA983867B (en) | 1997-05-16 | 1998-11-13 | Henkel Corp | Lithium and vanadium containing sealing composition and process therewith |
US6315823B1 (en) | 1998-05-15 | 2001-11-13 | Henkel Corporation | Lithium and vanadium containing sealing composition and process therewith |
JP3490021B2 (en) * | 1998-09-08 | 2004-01-26 | 日本パーカライジング株式会社 | Alkaline degreasing solution for metal material and method of using the same |
US6312812B1 (en) * | 1998-12-01 | 2001-11-06 | Ppg Industries Ohio, Inc. | Coated metal substrates and methods for preparing and inhibiting corrosion of the same |
JP3545974B2 (en) * | 1999-08-16 | 2004-07-21 | 日本パーカライジング株式会社 | Phosphate conversion treatment method for metal materials |
US6797387B2 (en) | 2000-09-21 | 2004-09-28 | Ppg Industries Ohio Inc. | Modified aminoplast crosslinkers and powder coating compositions containing such crosslinkers |
US20020179189A1 (en) | 2001-02-26 | 2002-12-05 | Nelson Homma | Process and composition for sealing porous coatings containing metal and oxygen atoms |
US7402214B2 (en) * | 2002-04-29 | 2008-07-22 | Ppg Industries Ohio, Inc. | Conversion coatings including alkaline earth metal fluoride complexes |
US7091286B2 (en) | 2002-05-31 | 2006-08-15 | Ppg Industries Ohio, Inc. | Low-cure powder coatings and methods for using the same |
US20040118483A1 (en) * | 2002-12-24 | 2004-06-24 | Michael Deemer | Process and solution for providing a thin corrosion inhibiting coating on a metallic surface |
TW200504243A (en) * | 2003-07-08 | 2005-02-01 | Nippon Paint Co Ltd | Inorganic-organic composite-treated zinc-plated steel sheet |
FR2863276B1 (en) | 2003-12-09 | 2006-01-20 | Snecma Moteurs | CHROMIUM-FREE HEXAVALENT-FREE CLAMPING METHOD AFTER SULFURIC ANODIZATION OF ALUMINUM ALLOYS, COLLAGE SOLUTION USED THEREIN, AND TREATED ARTICLE THEREFROM |
DE10358310A1 (en) * | 2003-12-11 | 2005-07-21 | Henkel Kgaa | Two-stage conversion treatment |
US20060054248A1 (en) * | 2004-09-10 | 2006-03-16 | Straus Martin L | Colored trivalent chromate coating for zinc |
US7452427B2 (en) * | 2004-12-01 | 2008-11-18 | Deft, Inc. | Corrosion resistant conversion coatings |
JP4242827B2 (en) * | 2004-12-08 | 2009-03-25 | 日本パーカライジング株式会社 | Metal surface treatment composition, surface treatment liquid, surface treatment method, and surface-treated metal material |
US20080138615A1 (en) * | 2005-04-04 | 2008-06-12 | Thomas Kolberg | Method for Coating Metallic Surfaces with an Aqueous Composition and Said Composition |
DE102005028145A1 (en) | 2005-06-17 | 2006-12-28 | Bayer Materialscience Ag | Optical data storage, its manufacture and use |
CA2619723C (en) * | 2005-08-19 | 2014-05-27 | Nippon Paint Co., Ltd. | Surface-conditioning composition, method for production thereof, and surface conditioning method |
ZA200807990B (en) | 2006-03-01 | 2009-12-30 | Chemetall Gmbh | Composition for metal surface treatment, metal surface treatment method, and metal material |
US8323470B2 (en) | 2007-08-15 | 2012-12-04 | Ppg Industries Ohio, Inc. | Electrodeposition coatings for use over aluminum substrates |
CN101519775B (en) * | 2008-02-28 | 2011-01-19 | 宝山钢铁股份有限公司 | Environmental-friendly chrome-free phosphating electrogalvanized sealed steel sheet and manufacturing method thereof |
US20110159315A1 (en) | 2008-05-27 | 2011-06-30 | Yuken Industry Co., Ltd. | Finishing Agent and Member Having an Overcoat Formed from the Finishing Agent |
DE102009007633B4 (en) * | 2009-02-05 | 2013-09-26 | Basf Coatings Ag | Multi-stage process for painting metallic substrates |
US9347134B2 (en) * | 2010-06-04 | 2016-05-24 | Prc-Desoto International, Inc. | Corrosion resistant metallate compositions |
CN101851755B (en) * | 2010-06-21 | 2013-01-09 | 山东省科学院新材料研究所 | Magnesium alloy chromium-free fluorine-free phosphorization solution and phosphorization method |
CN102677039B (en) * | 2012-05-21 | 2014-12-03 | 合肥工业大学 | Silane/rare-earth composite protective film on aluminum or aluminum alloy surface and preparation method thereof |
EP2859132B1 (en) * | 2012-06-08 | 2021-08-04 | PRC-Desoto International, Inc. | Indicator coatings for metal surfaces |
RU2611610C2 (en) * | 2012-08-29 | 2017-02-28 | Ппг Индастриз Огайо, Инк. | Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates |
US9303167B2 (en) * | 2013-03-15 | 2016-04-05 | Ppg Industries Ohio, Inc. | Method for preparing and treating a steel substrate |
RU2634808C2 (en) * | 2013-03-16 | 2017-11-03 | Прк-Десото Интернэшнл, Инк. | Cleaning compositions for metal substrates |
US9255332B2 (en) * | 2013-09-05 | 2016-02-09 | Ppg Industries Ohio, Inc. | Activating rinse and method for treating a substrate |
US10113070B2 (en) * | 2015-11-04 | 2018-10-30 | Ppg Industries Ohio, Inc. | Pretreatment compositions and methods of treating a substrate |
CN107345297B (en) * | 2015-12-10 | 2020-07-14 | 威海赤那思电子材料有限公司 | Alkaline cleaning solution, phosphating solution and metal surface treatment method |
US20170306498A1 (en) * | 2016-04-25 | 2017-10-26 | Ppg Industries Ohio, Inc. | Activating rinse and method for treating a substrate |
-
2017
- 2017-08-14 EP EP17755024.1A patent/EP3497263A1/en active Pending
- 2017-08-14 KR KR1020217038144A patent/KR102450429B1/en active IP Right Grant
- 2017-08-14 RU RU2019106622A patent/RU2751038C2/en active
- 2017-08-14 MX MX2019001708A patent/MX2019001708A/en unknown
- 2017-08-14 CN CN202110816347.3A patent/CN113621955A/en active Pending
- 2017-08-14 CN CN201780049474.7A patent/CN109642326A/en active Pending
- 2017-08-14 US US16/325,071 patent/US20210292907A1/en active Pending
- 2017-08-14 US US16/325,010 patent/US20190316261A1/en active Pending
- 2017-08-14 CN CN201780049426.8A patent/CN109563628A/en active Pending
- 2017-08-14 RU RU2019106619A patent/RU2722953C1/en active
- 2017-08-14 WO PCT/US2017/046730 patent/WO2018031992A1/en unknown
- 2017-08-14 CA CA3032156A patent/CA3032156A1/en not_active Abandoned
- 2017-08-14 MX MX2019001759A patent/MX2019001759A/en unknown
- 2017-08-14 CA CA3032691A patent/CA3032691C/en active Active
- 2017-08-14 KR KR1020197007118A patent/KR20190039560A/en not_active Application Discontinuation
- 2017-08-14 KR KR1020227039052A patent/KR102651352B1/en active IP Right Grant
- 2017-08-14 KR KR1020197007117A patent/KR20190039998A/en active Search and Examination
- 2017-08-14 EP EP17758336.6A patent/EP3497262A1/en active Pending
- 2017-08-14 WO PCT/US2017/046764 patent/WO2018031996A1/en unknown
-
2018
- 2018-02-09 KR KR1020227016305A patent/KR102650929B1/en active IP Right Grant
- 2018-02-09 WO PCT/US2018/017694 patent/WO2019036062A1/en unknown
- 2018-02-09 US US16/639,327 patent/US11725286B2/en active Active
- 2018-02-09 CN CN201880052767.5A patent/CN110997979A/en active Pending
- 2018-02-09 KR KR1020207007444A patent/KR102438452B1/en active IP Right Grant
- 2018-02-09 EP EP18705308.7A patent/EP3669016A1/en active Pending
- 2018-02-09 RU RU2020110559A patent/RU2744461C1/en active
- 2018-02-09 CA CA3072565A patent/CA3072565A1/en not_active Abandoned
- 2018-02-09 EP EP22164848.8A patent/EP4039853A1/en active Pending
- 2018-02-09 MX MX2020001747A patent/MX2020001747A/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6206982B1 (en) * | 1994-11-11 | 2001-03-27 | Commonwealth Scientific And Industrial Research Organisation | Process and solution for providing a conversion coating on a metal surface |
WO2014186286A1 (en) * | 2013-05-14 | 2014-11-20 | Prc-Desoto International, Inc. | Permanganate based conversion coating compositions |
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA3032691C (en) | Sealing composition | |
CA3031682C (en) | Systems and methods for treating a metal substrate | |
EP3497268B1 (en) | Methods for treating a metal substrate and substrate treated by the method | |
AU2017308214B2 (en) | Preparation of treatment composition and system and method of maintaining a treatment bath formed therefrom | |
US20210047737A1 (en) | System for Treating A Metal Substrate | |
KR20210126140A (en) | Sealing composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: PRC-DESOTO INTERNATIONAL, INC., CALIFORNIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MORRIS, ERIC L.;POST, GORDON L.;MAYO, MICHAEL A.;AND OTHERS;SIGNING DATES FROM 20170809 TO 20170810;REEL/FRAME:048390/0336 |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |