WO2023080918A1 - Corrosion resistant, chromium-free conversion coatings - Google Patents
Corrosion resistant, chromium-free conversion coatings Download PDFInfo
- Publication number
- WO2023080918A1 WO2023080918A1 PCT/US2022/021505 US2022021505W WO2023080918A1 WO 2023080918 A1 WO2023080918 A1 WO 2023080918A1 US 2022021505 W US2022021505 W US 2022021505W WO 2023080918 A1 WO2023080918 A1 WO 2023080918A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal
- chromium
- carboxylic
- free conversion
- salts
- Prior art date
Links
- 238000007739 conversion coating Methods 0.000 title claims abstract description 47
- 238000005260 corrosion Methods 0.000 title claims abstract description 34
- 230000007797 corrosion Effects 0.000 title claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 49
- 239000002184 metal Substances 0.000 claims abstract description 49
- 150000003839 salts Chemical class 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 22
- 150000001768 cations Chemical class 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 150000001450 anions Chemical class 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 3
- 229940095064 tartrate Drugs 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims 1
- 239000003112 inhibitor Substances 0.000 abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 10
- -1 carboxylate anion Chemical class 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 6
- 229910000838 Al alloy Inorganic materials 0.000 abstract description 5
- 239000003973 paint Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000010348 incorporation Methods 0.000 abstract description 3
- 229910045601 alloy Inorganic materials 0.000 abstract 1
- 239000000956 alloy Substances 0.000 abstract 1
- 150000007942 carboxylates Chemical class 0.000 description 11
- 229910052804 chromium Inorganic materials 0.000 description 11
- 239000011651 chromium Substances 0.000 description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 102100024106 Cyclin-Y Human genes 0.000 description 9
- 101000947157 Homo sapiens CXXC-type zinc finger protein 1 Proteins 0.000 description 9
- 101000910602 Homo sapiens Cyclin-Y Proteins 0.000 description 9
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 9
- 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 8
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 8
- GBYFRWZNEYJWAD-VTWSTLNFSA-N (3S,6S,12S,15S,21S,24S,30S,33S)-3,12,21,30-tetrabenzyl-1,4,10,13,19,22,28,31-octazapentacyclo[31.3.0.06,10.015,19.024,28]hexatriacontane-2,5,11,14,20,23,29,32-octone Chemical compound O=C1N[C@@H](Cc2ccccc2)C(=O)N2CCC[C@H]2C(=O)N[C@@H](Cc2ccccc2)C(=O)N2CCC[C@H]2C(=O)N[C@@H](Cc2ccccc2)C(=O)N2CCC[C@H]2C(=O)N[C@@H](Cc2ccccc2)C(=O)N2CCC[C@@H]12 GBYFRWZNEYJWAD-VTWSTLNFSA-N 0.000 description 4
- 229910000547 2024-T3 aluminium alloy Inorganic materials 0.000 description 4
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 101150014352 mtb12 gene Proteins 0.000 description 3
- 229920005646 polycarboxylate Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 229960001759 cerium oxalate Drugs 0.000 description 2
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- TVOIPJPTFTYKQM-UHFFFAOYSA-N propanedioic acid;zinc Chemical compound [Zn].OC(=O)CC(O)=O TVOIPJPTFTYKQM-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 230000000153 supplemental effect Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 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 1
- 241001163841 Albugo ipomoeae-panduratae Species 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
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 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 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 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 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000011885 synergistic combination Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229940068475 zinc citrate Drugs 0.000 description 1
- 235000006076 zinc citrate Nutrition 0.000 description 1
- 239000011746 zinc citrate Substances 0.000 description 1
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
-
- 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
- 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
- C23C22/46—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 oxalates
Definitions
- the invention constitutes the incorporation of corrosion inhibitor salts with at least one carboxylate anion and a variety of cations in conversion coatings for aluminum and aluminum alloys to enhance corrosion performance and paint adhesion.
- the inhibitor salts improve the corrosion resistance of these conversion coatings to a degree in which a chromium free conversion coating has the potential of meeting military specifications.
- Carboxylate salts with varying cations and anions have been evaluated in aluminum rich primers, proving to be effective at increasing corrosion resistance of the non-chromate primer. Additional research has been done in testing these inhibitors in aqueous solutions in an effort to increase corrosion performance of non-chromium conversion coatings. While salts with
- SUBSTITUTE SHEET (RULE 26) organic anions tend to incorporate well in organic primers, data suggests the salts in aqueous solutions provide a different mechanism in which they are providing corrosion resistance. Unlike paint systems, the quality of coatings formed by immersion in conversion coating is dependent on the substrates’ surface properties and the chemistries within the bath, leading to greater variability.
- SUBSTITUTE SHEET (RULE 26) chromium free coatings which are capable of providing corrosion protection similar to a chromium coating.
- hexavalent chromium (Cr6+) compounds such as sodium dichromate
- Cr6+-based conversion coatings to increase corrosion resistance and promote paint adhesion to the base substrate.
- Cr6+ compounds have established as being harmful to the environment and health, and to comply with the growing amount of regulations, efforts to reduce and replace hexavalent chromium in conversion coatings are increasing.
- NAWCAD developed TCP technology (trivalent chromium process), based on trivalent chromium (Cr3+). TCP has been successfully transitioned for many uses that were previously based on Cr6+. However, some users are pursuing total chromium-free metal finishing to more effectively comply with water treatment and other compliance regulations. Due to the demand for chromium-free conversion coatings many surface finishing companies are developing nonchromium conversion coatings but these products are significantly inferior at preventing corrosion to the current chromium (Cr6+ and Cr3+) conversion coatings.
- SUBSTITUTE SHEET (RULE 26) last no more than 2-4 days in neutral salt fog (ASTM B117) before showing significant signs of corrosion.
- a fluorozirconate-based conversion coating without any supplemental inhibitors will provide about 2 days of protection in neutral salt fog before exhibiting signs of corrosion. Adding certain carboxylate inhibitors to this base will increase its protection to 10 days in neutral salt fog, while other carboxylate inhibitors, some of which improve corrosion resistance in primers,
- SUBSTITUTE SHEET (RULE 26) will impair the corrosion performance, resulting in significant corrosion after 24 hours in salt fog.
- the object of the present invention is to provide a non-chromium rust preventive coating for metal such as aluminum which, is capable of corrosion resistance and does not allow development of white rust or pitting on aluminum.
- a further object is to provide a method of preventing rust and provide a rustpreventive chromium-free conversion coating.
- the process comprises coating the metal with a chromium-free conversion coating containing from about 4 to 8 grams of a metal fluorozirconate per liter of the chromium-free conversion coating and from about 0.5 to 5.0 grams of at least one carboxylic metal salt per liter of the chromium-free conversion coating.
- Figures 1a to 1e shows 2024-T3 aluminum as treated by Bonderite 5200 (3%) and of PPG X-bond (3% by volume) (1a) commercially available chromium-free conversion coating, a potassium hexafluorozirconate solution (1b) at a concentration of 6g/L, CFP1 (1c), CFP2 (1 d), and CFP3 (1e);
- Figure 2a shows the commercially available non-chromium conversion coating products, Bonderite 5200 (left and middle) and PPG X Bond (right panel, after 48 hours of salt fog (ASTM B117) exposure;
- FIGS. 2b-e show the potassium hexafluorozirconate solution (2b), CFP1 (2c), CFP2 (2d), and CFP3 (2e) after 48 hours of salt fog (ASTM B117) exposure;
- Figures 3a-c show 2024-T3 aluminum as treated by Bonderite 5200 at 3% (3a), CFP1 (3b) a chromium-free conversion coating containing potassium hexafluorozirconate (6 g/L) and zinc oxalate (1 .5g/L) and CFP4 (3c);
- Figure 4a shows the Bonderite 5200 panels after 24-hour exposure to ASTM B117.
- Figures 4b and 4c show the CFP1 and CFP4 panels, respectively, after 240 hour (10 days) exposure to ASTM B117.
- This invention is the incorporation of carboxylate metal salts in chromium-free conversion coatings for the purposes of increasing corrosion resistance.
- the compositions of the inhibitor salts are described as follows.
- Anions include the polycarboxylates chosen from linear and branched aliphatic molecules like oxalate, citrate, tartrate, succinate, malonate and adipate and the like.
- Cations include zinc, magnesium, manganese, calcium, strontium, zirconium, scandium, yttrium, lanthanum, and other lanthanides like cerium, praseodymium, neodymium, samarium, europium and gadolinium.
- the choice of anion and cation will influence water solubility as well as the reactivity with the other chemistries involved in the conversion coating solution and/or the metallic substrate.
- the carboxylate metal salts are added to the chromium-free conversion-free conversion coating in amounts ranging from about 0.5 to 5.0 grams per liter and may be added individually or in combination with other inhibitors.
- Carboxylate inhibitors may be blended with other carboxylate inhibitors using the same cation.
- zinc oxalate and zinc malonate may be blended, or they may be blended with different cations with the same or different anions.
- cerium oxalate and zinc oxalate or cerium oxalate and zinc malonate may be blended.
- Carboxylate inhibitors may also be combined with soluble inorganic salts with the
- SUBSTITUTE SHEET (RULE 26) same cation, such as zinc oxalate and zinc sulfate or they may be blended with different cations with different anions such as zinc oxalate and lithium phosphate.
- Inhibitors may also be blended with different molar ratios to obtain the maximum synergistic performance. This may range, but without limitation, from relatively low concentrations of a few milligrams per liter to beyond the super saturation point for the carboxylate inhibitor where no more can dissolve in solution.
- the present invention more specifically relates to synergistic metal polycarboxylate combinations and to methods of treating metal to improve the metal’s corrosion resistance.
- the method includes applying to the surface of metal, a chromium-free conversion coating which comprises an effective amount of a synergistic mixture of metal carboxylates.
- a synergistic blend of corrosion inhibitors consisting of at least two different metal carboxylates, such as polycarboxylics chosen from linear and branched aliphatic molecules like oxalate, succinate, and adipate, and aromatic molecules like phthalate, mellitate and trimellitate and the like. These are specific examples of some molecules.
- polycarboxylic acids which can be used for preparing the synergistic combination.
- the cations of the metal carboxylates are identified in the Periodic Table and include, for example, but without limitation, elements chosen from: Group la - Lithium, potassium and sodium; Group Ila - Magnesium, calcium, strontium, and barium; Group lllb - Scandium, yttium, lanthanum and the other lanthanides; Group IVb -Titanium and zirconium; Group Vb - Vanadium and
- SUBSTITUTE SHEET (RULE 26) niobium; Group Vlb - Chromium and molybdenum; Group Vllb - Manganese; Group VIII - Iron, cobalt and nickel; Group lb - Copper; Group lib - Zinc; Group Illa - Aluminum, and Group Va - Bismuth.
- Figures 1a-e show 2024-T3 aluminum as treated by Bonderite 5200 (3%) and of PPG X-bond (3% by volume) and with various additional coatings.
- Figure 1a shows the additional coating being a commercially available chromium-free conversion coating, while in Figure 1b it is a potassium hexafluorozirconate solution at a concentration of 6g/L., which is used as the base for the following conversion coating with inhibitors.
- CFP1 is used, which is a subject chromium-free conversion coating consisting of potassium hexafluorozirconate (6 g/L) and a zinc oxalate at a concentration of 1.5g/L.
- CFP2 is used.
- This is another chromium-free conversion coating, which contains potassium hexafluorozirconate (6 g/L) and zinc citrate (1.5 g/L) (the same concentration and cation as CFP1 but with a different carboxylate anion), and CFP3.
- SUBSTITUTE SHEET (RULE 26) were first cleaned for 10 minutes using an alkaline cleaner (Bonderite C-AK 6849 Aero at 18%) at 140° F, and then chemically deoxidized at room temperature for 1 min. using Bonderite C-1C SmutGo NO at 20%. All conversion coating solutions were at room temperature, approximately 75° Fahrenheit.
- This invention is directed to a method of providing chromate-free, conversion coatings when coated onto a metal substrate, such as aluminum or aluminum alloy substrates, said coatings are able to withstand hours of salt spray test without detectable corrosion on the metal. Moreover, the corrosion-inhibiting
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Process for treating metal such as aluminum and its alloys to prevent corrosion which comprises coating the metal with a chromium-free conversion composition containing effective amounts of metal fluorozirconates and carboxylic metal salts. The process comprises coating the metal with a chromium-free conversion coating containing from about 4 to 8 grams of a metal fluorozirconate per liter of the chromium-free conversion coating and from about 0.5 to 5.0 grams of at least one carboxylic metal salt per liter of the chromium-free conversion coating. The incorporation of corrosion inhibitor salts with at least one carboxylate anion and a variety of cations in conversion coatings for aluminum and aluminum alloys to enhance corrosion performance and paint adhesion.
Description
CORROSION RESISTANT, CHROMIUM-FREE
CONVERSION COATINGS
ORIGIN OF INVENTION
[0001] The invention described herein was made by employees of the United States Government and may be manufactured and used by or for the Government for governmental purposes without the payment of any royalties thereon or therefor.
FIELD OF THE INVENTION
[0002] The invention constitutes the incorporation of corrosion inhibitor salts with at least one carboxylate anion and a variety of cations in conversion coatings for aluminum and aluminum alloys to enhance corrosion performance and paint adhesion. The inhibitor salts improve the corrosion resistance of these conversion coatings to a degree in which a chromium free conversion coating has the potential of meeting military specifications.
[0003] Carboxylate salts with varying cations and anions have been evaluated in aluminum rich primers, proving to be effective at increasing corrosion resistance of the non-chromate primer. Additional research has been done in testing these inhibitors in aqueous solutions in an effort to increase corrosion performance of non-chromium conversion coatings. While salts with
1
SUBSTITUTE SHEET (RULE 26)
organic anions tend to incorporate well in organic primers, data suggests the salts in aqueous solutions provide a different mechanism in which they are providing corrosion resistance. Unlike paint systems, the quality of coatings formed by immersion in conversion coating is dependent on the substrates’ surface properties and the chemistries within the bath, leading to greater variability.
[0004] The novel features of these inhibitor salts are their carboxylate anions, which result in varying water solubility and therefore, seemingly altering the mechanism in which the coating is formed on the metallic substrate. Typical corrosion inhibitors will dissociate in solution and react with the metal substrate or bind to the primitive layers of the coatings. However, the low solubility of these salts and as analytical data indicates the salts may not deposit on the metal substrate in this manner.
BACKGROUND
[0005] Prior conversion coatings have used soluble inorganic salts as inhibitors but none so far have incorporated carboxylate salts. Due to the believed mechanism of conversion coating formation, it is not intuitive that insoluble or very slightly soluble compounds would outperform salts with the same cations with high solubility. Despite the developments of the prior art, the corrosion resistance by non-chromate treatments is less than that provided by chromate methods, particularly in the aircraft industries. This invention relates to
2
SUBSTITUTE SHEET (RULE 26)
chromium free coatings which are capable of providing corrosion protection similar to a chromium coating.
[0006] For decades, hexavalent chromium (Cr6+) compounds, such as sodium dichromate, have been used as corrosion inhibitors in surface finishing treatments on metallic substrates. Specifically, aluminum and aluminum alloys are often treated with Cr6+- based conversion coatings to increase corrosion resistance and promote paint adhesion to the base substrate. However, entities have established Cr6+ compounds as being harmful to the environment and health, and to comply with the growing amount of regulations, efforts to reduce and replace hexavalent chromium in conversion coatings are increasing.
[0007] In response to the need to eliminate the use of Cr6+, NAWCAD developed TCP technology (trivalent chromium process), based on trivalent chromium (Cr3+). TCP has been successfully transitioned for many uses that were previously based on Cr6+. However, some users are pursuing total chromium-free metal finishing to more effectively comply with water treatment and other compliance regulations. Due to the demand for chromium-free conversion coatings many surface finishing companies are developing nonchromium conversion coatings but these products are significantly inferior at preventing corrosion to the current chromium (Cr6+ and Cr3+) conversion coatings. While exact formulas are undisclosed, known non-chromium conversion coating solutions are either zirconium-based or cerium-based, and some contain a supplemental soluble, inorganic salt, such as zinc sulfate. Unpainted aluminum 2024 panels treated with these formulas, on average, will
3
SUBSTITUTE SHEET (RULE 26)
last no more than 2-4 days in neutral salt fog (ASTM B117) before showing significant signs of corrosion.
[0008] Based on the current state-of-the-art, there is still a strong need for chromium-free conversion coatings which perform similarly to Cr6+ and Cr3+ products, especially in corrosion resistance of “bare” or unpainted aluminum alloys. This requirement is critical for use in virtually all military and aviation applications and is included in military, commercial, and company specifications for conversion coatings.
[0009] Recent research and development in chromium-free conversion coating is based on the demand for superior products that could be used for bulk applications as well as for treatment of the aluminum powder used in Al-rich primers. One promising area of research is the polycarboxylate compounds used in Al-rich primers. These have demonstrated improvements in corrosion performance when combined in certain ratios and concentrations. These salts have also shown improvements in the corrosion resistance of flluorozirconate- based conversion coatings solutions despite their tendency to have low solubility. The fluorozirconates are added to the chromium-free conversion composition in amounts ranging from about 4 to 8 grams, e.g., grams per liter of the chromium- free composition. A fluorozirconate-based conversion coating without any supplemental inhibitors will provide about 2 days of protection in neutral salt fog before exhibiting signs of corrosion. Adding certain carboxylate inhibitors to this base will increase its protection to 10 days in neutral salt fog, while other carboxylate inhibitors, some of which improve corrosion resistance in primers,
4
SUBSTITUTE SHEET (RULE 26)
will impair the corrosion performance, resulting in significant corrosion after 24 hours in salt fog.
SUMMARY
[0010] The object of the present invention is to provide a non-chromium rust preventive coating for metal such as aluminum which, is capable of corrosion resistance and does not allow development of white rust or pitting on aluminum. A further object is to provide a method of preventing rust and provide a rustpreventive chromium-free conversion coating.
[0011] It is a feature of the invention to provide a process for treating metal surfaces to protect the metal from corrosion. The process comprises coating the metal with a chromium-free conversion coating containing from about 4 to 8 grams of a metal fluorozirconate per liter of the chromium-free conversion coating and from about 0.5 to 5.0 grams of at least one carboxylic metal salt per liter of the chromium-free conversion coating.
5
SUBSTITUTE SHEET (RULE 26)
DRAWINGS
[0012] Figures 1a to 1e shows 2024-T3 aluminum as treated by Bonderite 5200 (3%) and of PPG X-bond (3% by volume) (1a) commercially available chromium-free conversion coating, a potassium hexafluorozirconate solution (1b) at a concentration of 6g/L, CFP1 (1c), CFP2 (1 d), and CFP3 (1e);
Figure 2a shows the commercially available non-chromium conversion coating products, Bonderite 5200 (left and middle) and PPG X Bond (right panel, after 48 hours of salt fog (ASTM B117) exposure;
Figures 2b-e show the potassium hexafluorozirconate solution (2b), CFP1 (2c), CFP2 (2d), and CFP3 (2e) after 48 hours of salt fog (ASTM B117) exposure;
Figures 3a-c show 2024-T3 aluminum as treated by Bonderite 5200 at 3% (3a), CFP1 (3b) a chromium-free conversion coating containing potassium hexafluorozirconate (6 g/L) and zinc oxalate (1 .5g/L) and CFP4 (3c);
Figure 4a shows the Bonderite 5200 panels after 24-hour exposure to ASTM B117; and,
Figures 4b and 4c show the CFP1 and CFP4 panels, respectively, after 240 hour (10 days) exposure to ASTM B117.
6
SUBSTITUTE SHEET (RULE 26)
DESCRIPTION
[0013] This invention is the incorporation of carboxylate metal salts in chromium-free conversion coatings for the purposes of increasing corrosion resistance. The compositions of the inhibitor salts are described as follows. Anions include the polycarboxylates chosen from linear and branched aliphatic molecules like oxalate, citrate, tartrate, succinate, malonate and adipate and the like. Cations include zinc, magnesium, manganese, calcium, strontium, zirconium, scandium, yttrium, lanthanum, and other lanthanides like cerium, praseodymium, neodymium, samarium, europium and gadolinium. The choice of anion and cation will influence water solubility as well as the reactivity with the other chemistries involved in the conversion coating solution and/or the metallic substrate.
[0014] The carboxylate metal salts are added to the chromium-free conversion-free conversion coating in amounts ranging from about 0.5 to 5.0 grams per liter and may be added individually or in combination with other inhibitors. Carboxylate inhibitors may be blended with other carboxylate inhibitors using the same cation. For example, but without limitation, zinc oxalate and zinc malonate may be blended, or they may be blended with different cations with the same or different anions. Another example, but without limitation, cerium oxalate and zinc oxalate or cerium oxalate and zinc malonate may be blended. Carboxylate inhibitors may also be combined with soluble inorganic salts with the
7
SUBSTITUTE SHEET (RULE 26)
same cation, such as zinc oxalate and zinc sulfate or they may be blended with different cations with different anions such as zinc oxalate and lithium phosphate.
[0015] Inhibitors may also be blended with different molar ratios to obtain the maximum synergistic performance. This may range, but without limitation, from relatively low concentrations of a few milligrams per liter to beyond the super saturation point for the carboxylate inhibitor where no more can dissolve in solution.
[0016] The present invention more specifically relates to synergistic metal polycarboxylate combinations and to methods of treating metal to improve the metal’s corrosion resistance. The method includes applying to the surface of metal, a chromium-free conversion coating which comprises an effective amount of a synergistic mixture of metal carboxylates. More specifically, but without limitation, a synergistic blend of corrosion inhibitors, consisting of at least two different metal carboxylates, such as polycarboxylics chosen from linear and branched aliphatic molecules like oxalate, succinate, and adipate, and aromatic molecules like phthalate, mellitate and trimellitate and the like. These are specific examples of some molecules. There are many other polycarboxylic acids which can be used for preparing the synergistic combination.
[0017] The cations of the metal carboxylates are identified in the Periodic Table and include, for example, but without limitation, elements chosen from: Group la - Lithium, potassium and sodium; Group Ila - Magnesium, calcium, strontium, and barium; Group lllb - Scandium, yttium, lanthanum and the other lanthanides; Group IVb -Titanium and zirconium; Group Vb - Vanadium and
8
SUBSTITUTE SHEET (RULE 26)
niobium; Group Vlb - Chromium and molybdenum; Group Vllb - Manganese; Group VIII - Iron, cobalt and nickel; Group lb - Copper; Group lib - Zinc; Group Illa - Aluminum, and Group Va - Bismuth.
[0018] Figures 1a-e show 2024-T3 aluminum as treated by Bonderite 5200 (3%) and of PPG X-bond (3% by volume) and with various additional coatings. Figure 1a shows the additional coating being a commercially available chromium-free conversion coating, while in Figure 1b it is a potassium hexafluorozirconate solution at a concentration of 6g/L., which is used as the base for the following conversion coating with inhibitors. In Figure 1c, CFP1 is used, which is a subject chromium-free conversion coating consisting of potassium hexafluorozirconate (6 g/L) and a zinc oxalate at a concentration of 1.5g/L., while in Figure 1d CFP2 is used. This is another chromium-free conversion coating, which contains potassium hexafluorozirconate (6 g/L) and zinc citrate (1.5 g/L) (the same concentration and cation as CFP1 but with a different carboxylate anion), and CFP3. In Figure 1e, another chromium-free conversion coating I is used, also containing potassium hexafluorozirconate (6 g/L) and calcium oxalate (1.5 g/L) (the same concentration and carboxylate anion as CFP1 but a different cation).
[0019] For Figure 1a, the left and middle panels were immersed for 2 minutes in the Bonderite 5200, the left panel had a final rinse after the coating, the middle was dry-in-place. The right panel was immersed in PPG X-Bond for 5 minutes with a final rinse. For Figures 1 b-1 e, panels were immersed for, from left to right, 5, 10, and 15 minutes in their respective conversion coatings. All panels
9
SUBSTITUTE SHEET (RULE 26)
were first cleaned for 10 minutes using an alkaline cleaner (Bonderite C-AK 6849 Aero at 18%) at 140° F, and then chemically deoxidized at room temperature for 1 min. using Bonderite C-1C SmutGo NO at 20%. All conversion coating solutions were at room temperature, approximately 75° Fahrenheit.
[0020] According to this set of neutral salt fog data, it is evident that both the carboxylate anion and cation of the inhibitor contribute to the corrosion protection of the substrate. Further salt fog testing was done using zinc oxalate, Figures 3a - c below show 2024-T3 aluminum as treated by Bonderite 5200 at 3% (Figure 3a), CFP1 (Figure 3b) a chromium-free conversion coating containing potassium hexafluorozirconate (6 g/L) and zinc oxalate (1.5g/L), and CFP4 (Figure 3c), the same as CFP1 but with a different doubled concentration of zinc oxalate (3g/L). For Figure 3a, from left to right, panels were immersed for 2, 5 and 10 minutes in the Bonderite 5200. For Figures 3b and 3c, the left panels were immersed for 5 minutes in the CFP and the middle and right panels for 10 minutes. All panels were first cleaned for 10 minutes using an alkaline cleaner (Bonderite C-AK 6849 Aero at 18%) at 140°F and then chemically deoxidized at room temperature for 1 min. using Bonderite C-1C SmutGo NC at 20%. All conversion coating solutions were at room temperature, approximately 75° Fahrenheit.
[0021] This invention is directed to a method of providing chromate-free, conversion coatings when coated onto a metal substrate, such as aluminum or aluminum alloy substrates, said coatings are able to withstand hours of salt spray test without detectable corrosion on the metal. Moreover, the corrosion-inhibiting
10
SUBSTITUTE SHEET (RULE 26)
methods do not cause the health hazards associated with hexavalent chromates coatings.
[0022] While this invention has been described by a number of specific examples, it is obvious that there are other variations and modifications which can be made without departing from the spirit and scope of the invention as particularly set forth in the appended claims.
11
SUBSTITUTE SHEET (RULE 26)
Claims
1. A process for treating metal surfaces to protect the metal from corrosion which comprises coating the metal with a chromium-free conversion coating containing from about 4 to 8 grams of a metal fluorozirconate per liter of the chromium-free conversion coating and from about 0.5 to 5.0 grams of at least one carboxylic metal salt per liter of the chromium-free conversion coating.
2. The process of claim 1 , wherein at least one of the carboxylic metal salts has an anion or cation different from the other carboxylic metal salts.
3. The process of claim 2, wherein the cation of the carboxylic metal salt is a metal selected from Group II of the Periodic Table.
4. The process of claim 2, wherein the anion of the carboxylic metal salt is selected from the group consisting of oxalate, tartrate, succinate, adipate, phthalate, mellitate and trimellilate.
5. The process of claim 4, wherein one of the carboxylic metal salts is a metal succinate.
12
SUBSTITUTE SHEET (RULE 26)
6. The process of claim 4, wherein one of the carboxylic metal salts is a metal oxalate.
7. The process of claim 4, wherein one of the carboxylic metal salts is a metal phthalate.
8. The process of claim 4, wherein the metal is selected from the Periodic Table.
9. The process of claim 4, wherein the metal is selected from Group II of the Period Table.
10. The process of claim 1 , wherein the carboxylic metal salt is a polycarboxylic metal salt.
11. The process of claim 10, wherein at least one polycarboxylic metal salt has a cation different from the other carboxylic metal salts.
13
SUBSTITUTE SHEET (RULE 26)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17/517,715 US20230136068A1 (en) | 2021-11-03 | 2021-11-03 | Corrosion resistant chromium free conversion coatings |
US17/517,715 | 2021-11-03 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2023080918A1 true WO2023080918A1 (en) | 2023-05-11 |
Family
ID=86145495
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2022/021505 WO2023080918A1 (en) | 2021-11-03 | 2022-03-23 | Corrosion resistant, chromium-free conversion coatings |
Country Status (2)
Country | Link |
---|---|
US (1) | US20230136068A1 (en) |
WO (1) | WO2023080918A1 (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20150020925A1 (en) * | 2012-02-10 | 2015-01-22 | Mecaprotec Industries | Method for the surface treatment of parts made of an aluminum or magnesium alloy |
US10351715B2 (en) * | 2017-03-30 | 2019-07-16 | The United States Of America As Represented By The Secretary Of The Navy | Synergistic metal polycarboxylate corrosion inhibitors |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008174807A (en) * | 2007-01-19 | 2008-07-31 | Nippon Hyomen Kagaku Kk | Chromium-free metal surface treatment liquid |
-
2021
- 2021-11-03 US US17/517,715 patent/US20230136068A1/en not_active Abandoned
-
2022
- 2022-03-23 WO PCT/US2022/021505 patent/WO2023080918A1/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20150020925A1 (en) * | 2012-02-10 | 2015-01-22 | Mecaprotec Industries | Method for the surface treatment of parts made of an aluminum or magnesium alloy |
US10351715B2 (en) * | 2017-03-30 | 2019-07-16 | The United States Of America As Represented By The Secretary Of The Navy | Synergistic metal polycarboxylate corrosion inhibitors |
Also Published As
Publication number | Publication date |
---|---|
US20230136068A1 (en) | 2023-05-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7776448B2 (en) | Conversion coatings including alkaline earth metal fluoride complexes | |
EP1404894B1 (en) | Corrosion resistant coatings for aluminum and aluminum alloys | |
US5294266A (en) | Process for a passivating postrinsing of conversion layers | |
EP1841898B1 (en) | Rinsable metal pretreatment methods and compositions | |
EP1853750B1 (en) | Process for sealing phosphoric acid anodized aluminums | |
US6361833B1 (en) | Composition and process for treating metal surfaces | |
CA2472562C (en) | Non-carcinogenic corrosion inhibiting additive | |
CA2420587A1 (en) | Surface preparation agent and surface preparation method | |
CA2349376A1 (en) | Composition and process for treating metal surfaces | |
US6749694B2 (en) | Conversion coatings including alkaline earth metal fluoride complexes | |
GB2046312A (en) | Processes and compositions for coating metal surfaces | |
JP2008115442A (en) | Aluminum plated steel material having excellent discoloration resistance upon heating and corrosion resistance after heating, and water-based treating agent therefor | |
JPH04276087A (en) | Method for after-cleaning of formed layer | |
CA2018631C (en) | Process for a passivating postrinsing of phosphate layers | |
WO2013183644A1 (en) | Trivalent chromium-conversion processing solution containing aluminum-modified colloidal silica | |
JP5549837B2 (en) | Rust treatment solution for rust prevention of chromium plating film and rust prevention treatment method | |
US20230136068A1 (en) | Corrosion resistant chromium free conversion coatings | |
CA2169193A1 (en) | Process for treating zinciferous surfaces | |
CN113544312A (en) | Corrosion-proof treatment liquid and its use | |
CN104328420A (en) | Preparation method for chromium-free passivating solution for aviation aluminium alloy | |
CN104947098A (en) | Hot galvanizing chromium-free passivation agent and preparation method thereof | |
CN104342691A (en) | Zinc-coated steel plate surface passivation technology | |
CN104328421A (en) | Aviation aluminium alloy chromium-free passivation process | |
CN109609939B (en) | Film pretreatment agent composition | |
US9228263B1 (en) | Chemical conversion coating for protecting magnesium alloys from corrosion |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
NENP | Non-entry into the national phase |
Ref country code: DE |