US20060180247A1 - Process for preparing chromium conversion coatings for iron and iron alloys - Google Patents
Process for preparing chromium conversion coatings for iron and iron alloys Download PDFInfo
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- US20060180247A1 US20060180247A1 US11/076,106 US7610605A US2006180247A1 US 20060180247 A1 US20060180247 A1 US 20060180247A1 US 7610605 A US7610605 A US 7610605A US 2006180247 A1 US2006180247 A1 US 2006180247A1
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- grams
- water soluble
- iron
- aqueous solution
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- 229910000640 Fe alloy Inorganic materials 0.000 title claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 13
- 238000007739 conversion coating Methods 0.000 title claims description 11
- 239000011651 chromium Substances 0.000 title claims description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 8
- 229910052804 chromium Inorganic materials 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000000243 solution Substances 0.000 claims abstract description 38
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 37
- 230000008569 process Effects 0.000 claims abstract description 37
- 239000010959 steel Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000007864 aqueous solution Substances 0.000 claims abstract description 30
- -1 tetrafluoroborate Chemical compound 0.000 claims abstract description 30
- 238000005260 corrosion Methods 0.000 claims abstract description 24
- 230000007797 corrosion Effects 0.000 claims abstract description 24
- 230000002378 acidificating effect Effects 0.000 claims abstract description 18
- 239000002562 thickening agent Substances 0.000 claims abstract description 17
- 239000004094 surface-active agent Substances 0.000 claims abstract description 16
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 14
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 11
- 150000004761 hexafluorosilicates Chemical class 0.000 claims abstract description 9
- 238000004026 adhesive bonding Methods 0.000 claims abstract 3
- 239000000203 mixture Substances 0.000 claims description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 10
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 10
- 229960001763 zinc sulfate Drugs 0.000 claims description 10
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 10
- 150000001844 chromium Chemical class 0.000 claims description 9
- VVXLFFIFNVKFBD-UHFFFAOYSA-N 4,4,4-trifluoro-1-phenylbutane-1,3-dione Chemical group FC(F)(F)C(=O)CC(=O)C1=CC=CC=C1 VVXLFFIFNVKFBD-UHFFFAOYSA-N 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 239000003093 cationic surfactant Substances 0.000 claims description 4
- JUVGUSVNTPYZJL-UHFFFAOYSA-N chromium zirconium Chemical compound [Cr].[Zr] JUVGUSVNTPYZJL-UHFFFAOYSA-N 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 3
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- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
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- 238000000576 coating method Methods 0.000 abstract description 38
- 239000011248 coating agent Substances 0.000 abstract description 25
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- 229910045601 alloy Inorganic materials 0.000 description 12
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- 229910052751 metal Inorganic materials 0.000 description 6
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- 229910019142 PO4 Inorganic materials 0.000 description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- SKJCKYVIQGBWTN-UHFFFAOYSA-N (4-hydroxyphenyl) methanesulfonate Chemical compound CS(=O)(=O)OC1=CC=C(O)C=C1 SKJCKYVIQGBWTN-UHFFFAOYSA-N 0.000 description 1
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- 241000416162 Astragalus gummifer Species 0.000 description 1
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- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
Definitions
- This invention relates to a process for preparing zirconium-chromium conversion coatings on iron and iron alloys.
- the process comprises pretreating iron and its alloys with effective amounts of an acidic aqueous solution containing trivalent chromium compounds, at least one hexafluorozirconate and optionally, tetrafluoroborates and/or hexafluorosilicates, zinc compounds, surfactants, wetting agents and/or thickeners. More specifically, this invention relates to a process for pretreating iron and iron alloys to improve the alloys adhesion bonding and corrosion resistant properties.
- the process comprises treating iron and its alloys with an acidic aqueous solution containing effective amounts of at least one water-soluble trivalent chromium compound, a water soluble alkali metal hexafluorozirconate,.at least one water soluble alkali metal tetrafluoroborate and/or hexafluorosilicate, at least one water soluble divalent zinc compound, and effective amounts of water soluble thickeners and/or water soluble surfactants.
- a chemical pretreatment for iron alloys e.g. steel that is analogous to an aluminum pretreatment is not available but would be desirable. Such a coating would impart good paint adhesion to the steel substrate without needing a grit-blasted surface and thereby increase the corrosion resistance of the painted steel.
- a pretreatment of the alloy would also serve to prevent flash-rusting and allow for expanded handling times of the steel parts before they need to be painted. Such a pretreatment could be produced by merely immersing the components or steel parts in a tank of the pretreating solution, or by spraying the solution onto the alloy, or by wiping the solution on to the alloy.
- This invention relates to a process for preparing conversion coatings on iron and its alloys at ambient temperatures or higher e.g. ranging up to about 120° F. More specifically, this invention relates to a process of preparing conversion coatings on iron alloys such as steel to improve its corrosion resistance and adhesion bonding properties.
- the trivalent chromium process (TCP) of this invention comprises an acidic aqueous solution having a pH ranging from about 2.5 to 5.5 and preferably 3.7 to 4.0, and per liter of said acidic solution, from about 0.01 to 22 grams of a water soluble trivalent chromium compound, about 0.01 to 12 grams of an alkali metal hexafluorozirconate, from 0.0 to 12 grains of at least one fluorocompound selected from the group consisting of tetrafluoroborates, hexafluorosilicates and various combinations thereof in any ratio, from 0.0 to 10 grams of at least one water soluble divalent zinc compound, from 0.0 to 10 grams and preferable 0.5 to 1.5 grams of at least one water-soluble thickener, and/or from 0.0 to 10 and preferably 0.5 to 1.5 grams of at least one water soluble non-ionic, cationic or anionic surfactant or wetting agent.
- the pretreatment process of this invention also provides improved corrosion resistance of painted steel compared to steel that is painted by the direct-to-metal method.
- FIG. 1 is a photo of MIL-C-53022 primer on steel, with no grit blast.
- FIG. 2 is a photo of MIL-C-53022 primer on steel with TCP-P coating, with no grit blast.
- FIG. 3 is a photo of MW-C-53022 primer on steel with Aqua Zen treatment, with no grit blast.
- FIG. 4 is a photo of MIL-C-53022 primer on steel with grit blast treatment.
- FIG. 5 is a photo of MIL-C-53022 primer on steel with TCP-P coating with grit blast treatment.
- FIG. 6 is a photo of MIL-C-53022 primer on steel with Aqua Zen treatment with grit blast treatment.
- This invention relates to the process of using an acidic aqueous solution having a pH ranging from about 2.5 to 5.5, and preferably from about 2.5 to 4.5 or 3.7 to 4.0 for preparing a zirconium-chromium conversion coating on iron and its alloys such as steel to improve adhesion bonding and the corrosion-resistance properties of the alloy.
- the process comprises preparing the pretreatment coating by using an acidic aqueous solution at temperatures ranging up to about 120° F. or higher which comprises from about 0.01 to 22 grams and preferably from about 0.01 to 10 grams e.g. 5.0 to 7.0 grams of at least one water soluble trivalent chromium compound e.g.
- chromium sulfate about 0.01 to 12 grams and preferably about 1.0 to 8.0 grams e.g. 6.0 to 8.0 grams of at least one alkali metal hexafluorozirconate, about 0.0 to 12 grams and preferably from about 0.01 to 1.2 grams e.g. 0.12 to 0.24 grams of at least one fluorocompound selected from the group consisting of alkali metal tetrafluoroborates, alkali metal hexafluorosilicates and various mixtures or combinations thereof in any ratio, and from about 0.0 to 10 grams and preferably 0.001 to 10 or 0.1 to 5.0 grams of at least one divalent zinc compound such as zinc sulfate.
- the solution is applied at about room temperature to the substrate via immersion, spray or wipe-on techniques similar to the process used for aluminum pretreatments.
- Solution dwell time ranges from about 1.0 to 10 minutes. With this solution, the 1.0 to 10 minute dwell time yields an optimum film for color change, paint adhesion, and corrosion resistance. More importantly for this invention, the 1.0 to 10 minute dwell time yields appreciable color change to the as-deposited coating that ranges from royal blue to blue-gray depending primarily on the chemical composition of the aqueous solution.
- the remaining unreacted solution is subsequently rinsed from the substrate with tap or deionized water. No additional post-treatments of the alloy are necessary. The pretreatment coating is allowed to dry thoroughly before subsequent painting.
- an unique feature is the addition of a thickener to the solution that aids in optimum film formation during spray and wipe-on applications by slowing down solution evaporation. This also mitigates the formation of powdery deposits that degrade paint adhesion.
- the addition of thickeners also aids in proper film formation during large area applications and mitigates the diluent effect of rinse water that remains on the substrate during processing from previous steps. This feature of the process yields films that have no streaks and are an improvement in coloration and corrosion protection.
- Water-soluble thickeners such as the cellulose compounds are present in the acidic aqueous solution in amounts ranging from about 0.0 to 10 grams per liter and preferably 0.5 to 1.5 e.g., or about 1.0 gram per liter of the aqueous solution.
- an effective but small amount of at least one water-soluble surfactant or wetting agent can be added to the acidic solution in amounts ranging from about 0.0 to 10 grams and preferably from 0.5 to 1.5 grams e.g. 1.0 gram per liter of the acidic solution.
- water soluble surfactants known in the prior art and therefore for purpose of this invention the surfactants can be selected from the group consisting of non-ionic, cationic and anionic surfactants.
- the trivalent chromium is added to the solution as a water-soluble trivalent chromium compound, preferably as a trivalent chromium salt.
- the chromium salt can be added conveniently to the solution in its water soluble form wherein the valence of the chromium is plus 3.
- some of the preferred chromium compounds are incorporated in the solution in the form of Cr 2 (SO 4 ) 3 , (NR 4 )Cr(SO 4 ) 2 or KCr(SO 4 ) 2 and any mixtures of these compounds.
- a preferred trivalent chromium salt concentration is within the range of about 5.0 to 7.0 grams per liter of the aqueous solution. It has been found that particularly good results are obtained from these processes when the trivalent chromium compound is present in solution in the preferred ranges.
- the alkali metal tetrafluoroborates and/or hexafluorosilicates can be added to the acidic solutions in amounts as low as 0.01 grams per liter up to the solubility limits of the compounds.
- about 50% weight percent of the fluorosilicate is added based on the weight of the fluorozirconate.
- about 4.0 grams per liter of fluorosilicate is added to the solution.
- An alternative is to add about 0.01 to 100 weight percent of the fluoroborate salt based on the weight of the fluorozirconate salt.
- the fluoroborate salt can be added based on the weight of the fluorozirconate salt.
- a specific example comprises from about 6.0 to 8.0 grams per liter of potassium hexafluorozirconate, about 5.0 to 7.0 grams per liter of chromium III sulfate basic, about 0.1 to 5.0 grams per liter of divalent zinc sulfate and about 0.12 to 0.24 grams per liter of potassium tetrafluoroborate and/or hexafluorosilicate.
- An important result of the addition of the stabilizing additives i.e. the fluoroborates and/or fluorosilicates is that the solution is stable while the pH is maintained between about 2.5 and 5.5.
- the solutions may require small adjustments to the pH by the addition of effective amounts of a dilute acid or base to maintain the pH in the range of about 2.5 to 5.5 and preferably from 2.5 to 4.5 or 3.7 to 4.0.
- the solution may contain at least one divalent zinc compound to improve the color and corrosion protection of the alloy when compared to other treatment or compositions that do not contain zinc.
- the amount of the zinc compounds can be varied to adjust the color imparted to the coating, from as little as about 0.001 grams per liter up to 10 grams per liter e.g. 0.1 to 5.0 grams of Zinc 2 +cation.
- the divalent zinc can be supplied by any chemical compound e.g. salt that dissolves in water and is compatible with the other components in the acid solution.
- Divalent zinc compounds that are water soluble at the required concentrations preferably include, for example, zinc acetate, zinc telluride, zinc tetrafluoroborate, zinc molybdate, zinc hexafluorosilicate, zinc sulfate and the like or any combination thereof in any ratio.
- the pretreatment of the iron alloys can be carried out at various temperatures including the temperature of the solution which ranges from ambient e.g. from about room temperature up to about 120° F. or higher up to about 200° F. Room temperature is preferred, however, in that this eliminates the necessity for heating equipment.
- the coating may be air dried by any of the methods known in the art including, for example, oven drying, forced-air drying, exposure to infra-red lamps, and the like.
- the term “iron alloys” includes any iron alloy such as steel containing small but effective amounts of various other metals and non-metals such as carbon.
- a stable acidic aqueous solution having a pH ranging from about 3.4 to 4.0 for pretreating steel to provide a corrosion-resistant and a color recognized coating thereon comprises, per liter of solution, about 3.0 grams of trivalent chromium sulfate basic, about 4.0 grams of potassium hexafluorozirconate and about 1.0 gram of zinc sulfate.
- a stable acidic aqueous solution for treating steel to form a corrosion-resistant coating thereon comprises, per liter of solution, about 3.0 grams of trivalent chromium sulfate basic, about 4.0 grams of potassium hexafluorozirconate, and from about 0.0 to 0.12 grams of potassium tetrafluoroborate.
- a stable acidic aqueous solution for treating steel to provide a corrosion-resistant and a color recognized coating thereon comprises, per liter of solution, about 3.0 grams of trivalent chromium sulfate basic, about 4.0 grams of potassium hexafluorozirconate, about 0.12 grams of potassium tetrafluoroborate and about 2.0 grams of divalent zinc sulfate.
- Test coupons made from 4130 steel were cleaned in a standard alkaline cleaner (Turco HTC) at 140-160° F. for 10 minutes. Coupons were then rinsed and immersed directly into the test solution.
- the solution comprised an aqueous solution of about 6.0 grams per liter of chromium sulfate basic and 8.0 grams per liter of potassium hexafluorozirconate (TCP-P). Coupons were allowed to dwell in the the TCP-P for approximately 10 minutes, removed, and then thoroughly rinsed in de-ionized water. Coupons were then allowed to dry in a rack at ambient conditions. The resulting coatings were a deep royal blue in color, easily visible from across the laboratory. This is a critical indication for quality control during processing so that the processors have a way of telling that the coating is complete.
- control sets of 4130 were prepared by cleaning (Turco HTC) in the above-identified solution.
- a subset of these steel panels or coupons were grit blasted with alumina grit media to produce an average profile of 1.0 to 1.5 mils, a standard for a direct-to-metal painting.
- These steel coupons were then painted with MIL-C-53022 primer to approximately 1.0 mil thick.
- One sub-set of coupons was painted with Aqua Zen “wash primer” before the primer.
- the Aqua Zen is an industry standard coating used to promote adhesion and improve corrosion performance of the coating system.
- the painted coupons sat for 14 days at ambient conditions to allow the paint to cure. After curing, the coupons were subjected to painted adhesion and painted corrosion tests.
- Table 1 describes the paint adhesion results. Ratings of 4 and 5 are considered passing, and 0 to 3 are failing. As shown by the data, TCP-P coating provides excellent paint adhesion to the 4130 steel whether or not the steel was grit blasted. The TCP-P coating also shows better overall performance in comparison to the two controls panels which are commonly used on DoD equipment. In this test, the TCP-P coating is a better alternative to the Aqua Zen treatment and shows excellent performance with the MIL-C-53022 primer without the grit blast, where paint adhesion is very poor with only the primer. FIGS. 1 through 6 (photos) show examples of 7-day wet-tape adhesion for each coating system described in Table 1.
- Test coupons were prepared by the same process as in Example A.
- the composition (TCP-CC) solution comprised 3.0 grams per liter of chromium sulfate basic, 6.0 grams per liter of potassium hexafluorozirconate, 0.18 grams per liter of potassium tetrafluoroborate, and 2.0 grams per liter of zinc sulfate.
- Table 2 sets-forth the paint adhesion results from these coated coupons that are comparable to the results in Table 1.
- TCP-CC color change composition
- Table 2 sets-forth the paint adhesion results from these coated coupons that are comparable to the results in Table 1.
- TCP-CC color change composition
- the water soluble surfactants can be added to the trivalent chromium solutions in amounts ranging from about 0 to 10 grams per liter and preferably about 0.5 to 1.5 grams per liter.
- the surfactants are added to the aqueous solution to provide better wetting properties by lowering the surface tension thereby insuring complete coverage, and a more uniform film on the iron alloy substrates.
- the surfactants include at least one water soluble compound selected from the group consisting of non-ionic, anionic, and cationic surfactants.
- Some of the better known water soluble surfactants include the monocarboxyl imidoazoline, alkylsulfate sodium salts (DUPONOL®)), tridecyloxy poly(alkyleneoxy ethanol), ethoxylated or propoxylated alkylphenol (IGEPAL®), alkylsulfonamides, alkaryl sulfonates, palmiticaLkanol amides (CENTROL®), octylphenyl polyethoxy ethanol (TRITON®), sorbitan monopalmitate (SPAN®), dodecylphenyl polyethyleneglycol ether (e.g.
- alkyl pyrrolidone alkyl pyrrolidone
- polyalkoxylated fatty acid esters alkylbenzene sulfonates
- Other known water soluble surfactants include the alkylphenol alkoxylates, preferably the nonylphenol ethoxylates, and adducts of ethylene oxide with fatty amines; also see the publication: “Surfactants and Detersive Systems”, published by John Wiley & Sops in Kirk-Othmer's Encyclopedia of Chemical Technology, 3 rd Ed.
- thickening agents can be added to retain the aqueous solution on the surface for sufficient contact time.
- the thickeners employed are known inorganic and preferably the organic water soluble thickeners added to the trivalent chromium solutions in effective amounts e.g. at sufficient concentrations ranging from about 0 to 10 grams per liter and preferably 0.5 to 1.5 grams per liter of the acidic solution.
- Specific examples of some preferred thickeners include the cellulose compounds, e.g. hydroxypropyl cellulose (e.g. Klucel), ethyl cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, or methyl cellulose and mixtures thereof.
- Other water soluble inorganic thickeners include colloidal silica, clays such as bentonite, starches, gum arabic, tragacanth, agar and various combinations.
- the solution can be applied via immersion, spray or wipe-on techniques.
- the TCP solutions can be used at elevated temperatures ranging up to 65° C. or higher and optimally applied via immersion to further improve the corrosion resistance of the coatings.
- Solution dwell time ranges from about 1 to 60 minutes, and preferably 5 to 15 minutes at about 80° F. After dwelling, the remaining solution is then thoroughly rinsed from the substrate with tap or deionized water. No additional chemical manipulations of the deposited films are necessary for excellent performance. However, an application of a strong oxidizing solution can yield a film having additional corrosion resistance. The additional corrosion resistance is presumed to be due to the formation of hexavalent chromium in the film derived from the trivalent chromium.
- aqueous solutions may be sprayed from a spray tank apparatus designed to replace immersion tanks. This concept also reduces active chemical volume from about 1,000 gallons to about 30 to 50 gallons. Another feature of this invention is that this process provides coatings with corrosion resistance that is better or at least equivalent to other known coatings produced by sulfuric, chromic, or boric-sulfuric compositions.
Abstract
Description
- This Application is a Continuation-In-Part of copending Application Serial No. NC-96,347, Filed: , 2005.
- The invention described herein was made by employee(s) 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.
- This invention relates to a process for preparing zirconium-chromium conversion coatings on iron and iron alloys. The process comprises pretreating iron and its alloys with effective amounts of an acidic aqueous solution containing trivalent chromium compounds, at least one hexafluorozirconate and optionally, tetrafluoroborates and/or hexafluorosilicates, zinc compounds, surfactants, wetting agents and/or thickeners. More specifically, this invention relates to a process for pretreating iron and iron alloys to improve the alloys adhesion bonding and corrosion resistant properties. The process comprises treating iron and its alloys with an acidic aqueous solution containing effective amounts of at least one water-soluble trivalent chromium compound, a water soluble alkali metal hexafluorozirconate,.at least one water soluble alkali metal tetrafluoroborate and/or hexafluorosilicate, at least one water soluble divalent zinc compound, and effective amounts of water soluble thickeners and/or water soluble surfactants.
- Current surface preparation of iron alloys such as steel include a variety of mechanical and chemical processes, depending on the application. Phosphate coatings have been used historically to improve the adhesion of various outer coatings such as paint and corrosion resistance of steel. For. example, grit blasting has been used to improve the adhesion when phosphate coatings were not practical to apply. In this case, the desired paint primer is applied directly to the grit-blasted steel which is referred to as the “direct-to-metal” process. Many organizations rely on the direct-to-metal technique as the use of phosphate coatings decline due to their reliance on a hexavalent chromium “rinse” for optimum adhesion and corrosion resistance. While direct-to-metal coating is straightforward and does not rely on a chemically-produced coating, it does not, however, provide an optimum-performing coating system. The absence of a chemical pretreatment lowers the overall corrosion resistance of the system. This is partially due to the near ubiquitous use of non-chromated primers for painting iron alloys such as steel. In addition, while grit-blasting imparts a sound mechanical base for paint adhesion it is labor intensive and requires application of the grit over all the steel surface, generating large quantities of spent grit that must be collected and then recycled or disposed.
- Further, where there is no corrosion-resistant conversion coating on the iron alloys such as steel there is the problem of “flash rusting” that occurs after the steel parts are grit blasted or cleaned, but before the paint can be applied. The requirement to keep flash rust from occurring places a tremendous burden on scheduling and does not allow for components to sit for more than a few hours before being painted. This prevents the parts or components from being allowed to sit overnight or over the weekend and therefore prevents the work from being completed by the end of a shift where the parts cannot be painted before the end of a particular shift. This renders production less productive than it ordinarily could be. In addition, parts or components that are processed, but not yet painted that need to be shipped or moved before painting requires an elaborate and costly protective coating that must then be subsequently stripped before application of the paint. A chemical pretreatment for iron alloys e.g. steel that is analogous to an aluminum pretreatment is not available but would be desirable. Such a coating would impart good paint adhesion to the steel substrate without needing a grit-blasted surface and thereby increase the corrosion resistance of the painted steel. A pretreatment of the alloy would also serve to prevent flash-rusting and allow for expanded handling times of the steel parts before they need to be painted. Such a pretreatment could be produced by merely immersing the components or steel parts in a tank of the pretreating solution, or by spraying the solution onto the alloy, or by wiping the solution on to the alloy.
- This invention relates to a process for preparing conversion coatings on iron and its alloys at ambient temperatures or higher e.g. ranging up to about 120° F. More specifically, this invention relates to a process of preparing conversion coatings on iron alloys such as steel to improve its corrosion resistance and adhesion bonding properties. The trivalent chromium process (TCP) of this invention comprises an acidic aqueous solution having a pH ranging from about 2.5 to 5.5 and preferably 3.7 to 4.0, and per liter of said acidic solution, from about 0.01 to 22 grams of a water soluble trivalent chromium compound, about 0.01 to 12 grams of an alkali metal hexafluorozirconate, from 0.0 to 12 grains of at least one fluorocompound selected from the group consisting of tetrafluoroborates, hexafluorosilicates and various combinations thereof in any ratio, from 0.0 to 10 grams of at least one water soluble divalent zinc compound, from 0.0 to 10 grams and preferable 0.5 to 1.5 grams of at least one water-soluble thickener, and/or from 0.0 to 10 and preferably 0.5 to 1.5 grams of at least one water soluble non-ionic, cationic or anionic surfactant or wetting agent.
- It is therefore an object of this invention to provide an acidic aqueous solution comprising a trivalent chromium compound, hexafluorozirconates, and tetrafluoroborates and/or hexafluorosilicates for pretreating iron alloys to improve its adhesion and corrosion-resistance properties.
- It is another object of this invention to provide a stable acidic aqueous solution having a pH ranging from about 2.5 to 5.5 which comprises a trivalent chromium salt and hexafluorozirconates for pretreating iron alloys such as steel.
- It is another object of this invention to provide a pretreatment process for coating steel that has a practical color change and imparts good adhesion without a grit-blasted surface. The pretreatment process of this invention also provides improved corrosion resistance of painted steel compared to steel that is painted by the direct-to-metal method.
- It is a further object of this invention to provide a stable acidic aqueous solution having a pH ranging from about 3.7 to 4.0 comprising a trivalent chromium compound and hexafluorozirconates for treating iron alloys at about room temperature or higher wherein said acidic solution contains substantially no hexavalent chromium.
- These and other object of the invention will become apparent by reference to the detailed description when considered in conjunction with the accompanying
FIGS. 1-6 , (photos). -
FIG. 1 is a photo of MIL-C-53022 primer on steel, with no grit blast. -
FIG. 2 is a photo of MIL-C-53022 primer on steel with TCP-P coating, with no grit blast. -
FIG. 3 is a photo of MW-C-53022 primer on steel with Aqua Zen treatment, with no grit blast. -
FIG. 4 is a photo of MIL-C-53022 primer on steel with grit blast treatment. -
FIG. 5 is a photo of MIL-C-53022 primer on steel with TCP-P coating with grit blast treatment. -
FIG. 6 is a photo of MIL-C-53022 primer on steel with Aqua Zen treatment with grit blast treatment. - This invention relates to the process of using an acidic aqueous solution having a pH ranging from about 2.5 to 5.5, and preferably from about 2.5 to 4.5 or 3.7 to 4.0 for preparing a zirconium-chromium conversion coating on iron and its alloys such as steel to improve adhesion bonding and the corrosion-resistance properties of the alloy. The process comprises preparing the pretreatment coating by using an acidic aqueous solution at temperatures ranging up to about 120° F. or higher which comprises from about 0.01 to 22 grams and preferably from about 0.01 to 10 grams e.g. 5.0 to 7.0 grams of at least one water soluble trivalent chromium compound e.g. chromium sulfate, about 0.01 to 12 grams and preferably about 1.0 to 8.0 grams e.g. 6.0 to 8.0 grams of at least one alkali metal hexafluorozirconate, about 0.0 to 12 grams and preferably from about 0.01 to 1.2 grams e.g. 0.12 to 0.24 grams of at least one fluorocompound selected from the group consisting of alkali metal tetrafluoroborates, alkali metal hexafluorosilicates and various mixtures or combinations thereof in any ratio, and from about 0.0 to 10 grams and preferably 0.001 to 10 or 0.1 to 5.0 grams of at least one divalent zinc compound such as zinc sulfate.
- After cleaning and deoxidizing or pickling the iron alloy e.g. steel substrate via conventional mechanical or chemical techniques, the solution is applied at about room temperature to the substrate via immersion, spray or wipe-on techniques similar to the process used for aluminum pretreatments. Solution dwell time ranges from about 1.0 to 10 minutes. With this solution, the 1.0 to 10 minute dwell time yields an optimum film for color change, paint adhesion, and corrosion resistance. More importantly for this invention, the 1.0 to 10 minute dwell time yields appreciable color change to the as-deposited coating that ranges from royal blue to blue-gray depending primarily on the chemical composition of the aqueous solution. The remaining unreacted solution is subsequently rinsed from the substrate with tap or deionized water. No additional post-treatments of the alloy are necessary. The pretreatment coating is allowed to dry thoroughly before subsequent painting.
- In some processes, depending on the physical characteristics of the iron alloy i.e. steel substrate such as the physical size of the substrate, an unique feature is the addition of a thickener to the solution that aids in optimum film formation during spray and wipe-on applications by slowing down solution evaporation. This also mitigates the formation of powdery deposits that degrade paint adhesion. The addition of thickeners, also aids in proper film formation during large area applications and mitigates the diluent effect of rinse water that remains on the substrate during processing from previous steps. This feature of the process yields films that have no streaks and are an improvement in coloration and corrosion protection. Water-soluble thickeners such as the cellulose compounds are present in the acidic aqueous solution in amounts ranging from about 0.0 to 10 grams per liter and preferably 0.5 to 1.5 e.g., or about 1.0 gram per liter of the aqueous solution.
- Further, depending on the characteristics of the iron alloy, an effective but small amount of at least one water-soluble surfactant or wetting agent can be added to the acidic solution in amounts ranging from about 0.0 to 10 grams and preferably from 0.5 to 1.5 grams e.g. 1.0 gram per liter of the acidic solution. There are many water soluble surfactants known in the prior art and therefore for purpose of this invention the surfactants can be selected from the group consisting of non-ionic, cationic and anionic surfactants.
- The trivalent chromium is added to the solution as a water-soluble trivalent chromium compound, preferably as a trivalent chromium salt. Specifically, in formulating the acidic aqueous solutions of this invention, the chromium salt can be added conveniently to the solution in its water soluble form wherein the valence of the chromium is plus 3. For example, some of the preferred chromium compounds are incorporated in the solution in the form of Cr2(SO4)3, (NR4)Cr(SO4)2 or KCr(SO4)2 and any mixtures of these compounds. A preferred trivalent chromium salt concentration is within the range of about 5.0 to 7.0 grams per liter of the aqueous solution. It has been found that particularly good results are obtained from these processes when the trivalent chromium compound is present in solution in the preferred ranges.
- In some treatments, the alkali metal tetrafluoroborates and/or hexafluorosilicates can be added to the acidic solutions in amounts as low as 0.01 grams per liter up to the solubility limits of the compounds. For example, about 50% weight percent of the fluorosilicate is added based on the weight of the fluorozirconate. In other words, for 8.0 grams per liter of the fluorozirconate salt, about 4.0 grams per liter of fluorosilicate is added to the solution. An alternative is to add about 0.01 to 100 weight percent of the fluoroborate salt based on the weight of the fluorozirconate salt. For example, about 1.0 to 10 weight percent of the fluoroborate salt can be added based on the weight of the fluorozirconate salt. A specific example comprises from about 6.0 to 8.0 grams per liter of potassium hexafluorozirconate, about 5.0 to 7.0 grams per liter of chromium III sulfate basic, about 0.1 to 5.0 grams per liter of divalent zinc sulfate and about 0.12 to 0.24 grams per liter of potassium tetrafluoroborate and/or hexafluorosilicate. An important result of the addition of the stabilizing additives i.e. the fluoroborates and/or fluorosilicates is that the solution is stable while the pH is maintained between about 2.5 and 5.5. However, in some examples the solutions may require small adjustments to the pH by the addition of effective amounts of a dilute acid or base to maintain the pH in the range of about 2.5 to 5.5 and preferably from 2.5 to 4.5 or 3.7 to 4.0.
- The solution may contain at least one divalent zinc compound to improve the color and corrosion protection of the alloy when compared to other treatment or compositions that do not contain zinc. The amount of the zinc compounds can be varied to adjust the color imparted to the coating, from as little as about 0.001 grams per liter up to 10 grams per liter e.g. 0.1 to 5.0 grams of Zinc2+cation. The divalent zinc can be supplied by any chemical compound e.g. salt that dissolves in water and is compatible with the other components in the acid solution. Divalent zinc compounds that are water soluble at the required concentrations preferably include, for example, zinc acetate, zinc telluride, zinc tetrafluoroborate, zinc molybdate, zinc hexafluorosilicate, zinc sulfate and the like or any combination thereof in any ratio.
- The pretreatment of the iron alloys can be carried out at various temperatures including the temperature of the solution which ranges from ambient e.g. from about room temperature up to about 120° F. or higher up to about 200° F. Room temperature is preferred, however, in that this eliminates the necessity for heating equipment. The coating may be air dried by any of the methods known in the art including, for example, oven drying, forced-air drying, exposure to infra-red lamps, and the like. For purposes of this invention, the term “iron alloys” includes any iron alloy such as steel containing small but effective amounts of various other metals and non-metals such as carbon.
- The following Examples illustrate the stable solutions of this invention, and the method of using the solutions in providing color recognition, improved adhesion bonding and corrosion-resistant coatings for iron and its alloys.
- A stable acidic aqueous solution having a pH ranging from about 3.4 to 4.0 for pretreating steel to provide a corrosion-resistant and a color recognized coating thereon comprises, per liter of solution, about 3.0 grams of trivalent chromium sulfate basic, about 4.0 grams of potassium hexafluorozirconate and about 1.0 gram of zinc sulfate.
- A stable acidic aqueous solution for treating steel to form a corrosion-resistant coating thereon comprises, per liter of solution, about 3.0 grams of trivalent chromium sulfate basic, about 4.0 grams of potassium hexafluorozirconate, and from about 0.0 to 0.12 grams of potassium tetrafluoroborate.
- A stable acidic aqueous solution for treating steel to provide a corrosion-resistant and a color recognized coating thereon comprises, per liter of solution, about 3.0 grams of trivalent chromium sulfate basic, about 4.0 grams of potassium hexafluorozirconate, about 0.12 grams of potassium tetrafluoroborate and about 2.0 grams of divalent zinc sulfate.
- The following Examples and data in Tables 1 and 2 show the paint adhesion performance of coatings using Mil-P-53022 epoxy primer and 4130 steel test coupons. Mil-P-53022 primers are commonly used on steel in a variety of Department of Defense systems. It is evident from the data in the Tables that the coatings provide a substantial increase in paint adhesion compared to the control coatings. The compositions or solutions, though typically used at ambient conditions may be applied at elevated temperatures to increase the reaction rate.
- Process data and Examples for TCP/TCP-CC as a Conversion Coating for iron Alloys. Conversion coatings were applied to 4130 steel as follows:
- Test coupons made from 4130 steel were cleaned in a standard alkaline cleaner (Turco HTC) at 140-160° F. for 10 minutes. Coupons were then rinsed and immersed directly into the test solution. The solution comprised an aqueous solution of about 6.0 grams per liter of chromium sulfate basic and 8.0 grams per liter of potassium hexafluorozirconate (TCP-P). Coupons were allowed to dwell in the the TCP-P for approximately 10 minutes, removed, and then thoroughly rinsed in de-ionized water. Coupons were then allowed to dry in a rack at ambient conditions. The resulting coatings were a deep royal blue in color, easily visible from across the laboratory. This is a critical indication for quality control during processing so that the processors have a way of telling that the coating is complete.
- In addition to the TCP-P coated 4130 steel, control sets of 4130 were prepared by cleaning (Turco HTC) in the above-identified solution. A subset of these steel panels or coupons were grit blasted with alumina grit media to produce an average profile of 1.0 to 1.5 mils, a standard for a direct-to-metal painting. These steel coupons were then painted with MIL-C-53022 primer to approximately 1.0 mil thick. One sub-set of coupons was painted with Aqua Zen “wash primer” before the primer. The Aqua Zen is an industry standard coating used to promote adhesion and improve corrosion performance of the coating system. The painted coupons sat for 14 days at ambient conditions to allow the paint to cure. After curing, the coupons were subjected to painted adhesion and painted corrosion tests. Table 1 describes the paint adhesion results. Ratings of 4 and 5 are considered passing, and 0 to 3 are failing. As shown by the data, TCP-P coating provides excellent paint adhesion to the 4130 steel whether or not the steel was grit blasted. The TCP-P coating also shows better overall performance in comparison to the two controls panels which are commonly used on DoD equipment. In this test, the TCP-P coating is a better alternative to the Aqua Zen treatment and shows excellent performance with the MIL-C-53022 primer without the grit blast, where paint adhesion is very poor with only the primer.
FIGS. 1 through 6 (photos) show examples of 7-day wet-tape adhesion for each coating system described in Table 1.TABLE 1 COATINGS AND PAINT ADHESION RESULTS Coating Paint Adhesion Results Grit Blast System Dry 1-day Wet 4-day Wet 7-day Wet No MIL-C-53022 4 4 0 0 primer only No Aqua Zen 5 4 3 3 plus MIL-C- 53022 primer No TCP-P plus 5 4 4 4 MIL-C-53022 primer Yes MIL-C-53022 5 5 5 3 primer only Yes Aqua Zen 4 4 3 1 plus MIL-C- 53022 primer Yes TCP-P plus 5 5 5 4 MIL-C-53022 primer - Conversion coatings were applied to 4130 steel as follows:
- Test coupons were prepared by the same process as in Example A. The composition (TCP-CC) solution comprised 3.0 grams per liter of chromium sulfate basic, 6.0 grams per liter of potassium hexafluorozirconate, 0.18 grams per liter of potassium tetrafluoroborate, and 2.0 grams per liter of zinc sulfate.
- Table 2 sets-forth the paint adhesion results from these coated coupons that are comparable to the results in Table 1. As seen from the data, the coatings formed from this TCP i.e. color change composition (TCP-CC) performs as well as TCP-P as an adhesion promoter.
TABLE 2 PAINT ADHESION RESULTS FOR TCP-CC Coating Paint Adhesion Results Grit Blast System Dry 1-day Wet 4-day Wet 7-day Wet No TCP-CC plus 5 5 4 NA MIL-C-53022 primer Yes TCP-CC plus 5 5 5 NA MIL-C-53022 primer - In preparing the acidic solutions of this invention, the water soluble surfactants can be added to the trivalent chromium solutions in amounts ranging from about 0 to 10 grams per liter and preferably about 0.5 to 1.5 grams per liter. The surfactants are added to the aqueous solution to provide better wetting properties by lowering the surface tension thereby insuring complete coverage, and a more uniform film on the iron alloy substrates. The surfactants include at least one water soluble compound selected from the group consisting of non-ionic, anionic, and cationic surfactants. Some of the better known water soluble surfactants include the monocarboxyl imidoazoline, alkylsulfate sodium salts (DUPONOL®)), tridecyloxy poly(alkyleneoxy ethanol), ethoxylated or propoxylated alkylphenol (IGEPAL®), alkylsulfonamides, alkaryl sulfonates, palmiticaLkanol amides (CENTROL®), octylphenyl polyethoxy ethanol (TRITON®), sorbitan monopalmitate (SPAN®), dodecylphenyl polyethyleneglycol ether (e.g. TERGITROL®), alkyl pyrrolidone, polyalkoxylated fatty acid esters, alkylbenzene sulfonates and mixtures thereof. Other known water soluble surfactants include the alkylphenol alkoxylates, preferably the nonylphenol ethoxylates, and adducts of ethylene oxide with fatty amines; also see the publication: “Surfactants and Detersive Systems”, published by John Wiley & Sops in Kirk-Othmer's Encyclopedia of Chemical Technology, 3rd Ed.
- When large surfaces do not permit immersion or where vertical surfaces are to be sprayed, thickening agents can be added to retain the aqueous solution on the surface for sufficient contact time. The thickeners employed are known inorganic and preferably the organic water soluble thickeners added to the trivalent chromium solutions in effective amounts e.g. at sufficient concentrations ranging from about 0 to 10 grams per liter and preferably 0.5 to 1.5 grams per liter of the acidic solution. Specific examples of some preferred thickeners include the cellulose compounds, e.g. hydroxypropyl cellulose (e.g. Klucel), ethyl cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, or methyl cellulose and mixtures thereof. Other water soluble inorganic thickeners include colloidal silica, clays such as bentonite, starches, gum arabic, tragacanth, agar and various combinations.
- After preparing the iron alloy surface to be coated via conventional techniques, the solution can be applied via immersion, spray or wipe-on techniques. The TCP solutions can be used at elevated temperatures ranging up to 65° C. or higher and optimally applied via immersion to further improve the corrosion resistance of the coatings. Solution dwell time ranges from about 1 to 60 minutes, and preferably 5 to 15 minutes at about 80° F. After dwelling, the remaining solution is then thoroughly rinsed from the substrate with tap or deionized water. No additional chemical manipulations of the deposited films are necessary for excellent performance. However, an application of a strong oxidizing solution can yield a film having additional corrosion resistance. The additional corrosion resistance is presumed to be due to the formation of hexavalent chromium in the film derived from the trivalent chromium. The aqueous solutions may be sprayed from a spray tank apparatus designed to replace immersion tanks. This concept also reduces active chemical volume from about 1,000 gallons to about 30 to 50 gallons. Another feature of this invention is that this process provides coatings with corrosion resistance that is better or at least equivalent to other known coatings produced by sulfuric, chromic, or boric-sulfuric compositions.
- 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.
Claims (20)
Priority Applications (31)
Application Number | Priority Date | Filing Date | Title |
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US11/076,106 US20060180247A1 (en) | 2005-02-15 | 2005-02-15 | Process for preparing chromium conversion coatings for iron and iron alloys |
EP05851687A EP1848841B1 (en) | 2005-02-15 | 2005-11-14 | Composition and process for preparing chromium-zirconium coatings on metal substrates |
ES05851687T ES2413440T3 (en) | 2005-02-15 | 2005-11-14 | Composition and procedure for preparing chromium-zirconium coatings on metal substrates |
BRPI0519981A BRPI0519981B1 (en) | 2005-02-15 | 2005-11-14 | process for coating metallic substrates, and compositions for use in a process for coating metallic substrates |
CNA2005800483468A CN101142340A (en) | 2005-02-15 | 2005-11-14 | Process for preparing chromium conversion coatings for iron and iron alloys |
DK05851687.3T DK1848841T3 (en) | 2005-02-15 | 2005-11-14 | COMPOSITION AND PROCEDURE FOR PREPARING CHROME-ZIRCONIUM COATINGS ON METAL SUBSTRATES |
CA2597630A CA2597630C (en) | 2005-02-15 | 2005-11-14 | Composition and process for preparing protective coatings on metal substrates |
MX2007009803A MX2007009803A (en) | 2005-02-15 | 2005-11-14 | Composition and process for preparing chromium-zirconium coatings on metal substrates. |
CA002598397A CA2598397A1 (en) | 2005-02-15 | 2005-11-14 | Process for preparing chromium conversion coatings for iron and iron alloys |
AU2005327545A AU2005327545A1 (en) | 2005-02-15 | 2005-11-14 | Process for preparing chromium conversion coatings for iron and iron alloys |
ES05851727T ES2411429T3 (en) | 2005-02-15 | 2005-11-14 | Composition and procedure for preparing protective coatings on metal substrates |
EP05851727A EP1863952B1 (en) | 2005-02-15 | 2005-11-14 | Composition and process for preparing protective coatings on metal substrates |
CN2005800483449A CN101410550B (en) | 2005-02-15 | 2005-11-14 | Composition and process for preparing protective coatings on metal substrates |
JP2007555080A JP5060964B2 (en) | 2005-02-15 | 2005-11-14 | Composition and method for protective coating of metal substrates |
PCT/US2005/041414 WO2006088519A2 (en) | 2005-02-15 | 2005-11-14 | Composition and process for preparing chromium-zirconium coatings on metal substrates |
MX2007009801A MX2007009801A (en) | 2005-02-15 | 2005-11-14 | Composition and process for preparing protective coatings on metal substrates. |
KR1020077021173A KR20080000565A (en) | 2005-02-15 | 2005-11-14 | Composition and process for preparing chromium-zirconium coatings on metal substrates |
JP2007555078A JP5060963B2 (en) | 2005-02-15 | 2005-11-14 | Composition for coating chromium-zirconium on metal substrate and preparation method thereof |
PCT/US2005/041413 WO2006088518A2 (en) | 2005-02-15 | 2005-11-14 | Process for preparing chromium conversion coatings for iron and iron alloys |
CN2005800483472A CN101189073B (en) | 2005-02-15 | 2005-11-14 | Composition and process for preparing chromium-zirconium coatings on metal substrates |
KR1020077021175A KR20070118085A (en) | 2005-02-15 | 2005-11-14 | Process for preparing chromium conversion coatings for iron and iron alloys |
EP05851686A EP1848840A2 (en) | 2005-02-15 | 2005-11-14 | Process for preparing chromium conversion coatings for iron and iron alloys |
KR1020077021138A KR20080000564A (en) | 2005-02-15 | 2005-11-14 | Composition and process for preparing protective coatings on metal substrates |
BRPI0519957A BRPI0519957B1 (en) | 2005-02-15 | 2005-11-14 | process for coating metallic substrates and compositions for coating metallic substrates |
CA002598396A CA2598396A1 (en) | 2005-02-15 | 2005-11-14 | Composition and process for preparing chromium-zirconium coatings on metal substrates |
JP2007555077A JP2008530360A (en) | 2005-02-15 | 2005-11-14 | Method for preparing chromium conversion coatings for iron and iron alloys |
MX2007009798A MX2007009798A (en) | 2005-02-15 | 2005-11-14 | Process for preparing chromium conversion coatings for iron and iron alloys. |
AU2005327548A AU2005327548A1 (en) | 2005-02-15 | 2005-11-14 | Composition and process for preparing protective coatings on metal substrates |
PCT/US2005/041587 WO2006088521A2 (en) | 2005-02-15 | 2005-11-14 | Composition and process for preparing protective coatings on metal substrates |
DK05851727.7T DK1863952T3 (en) | 2005-02-15 | 2005-11-14 | COMPOSITION AND PROCEDURE FOR MANUFACTURING PROTECTIVE COATINGS ON METAL SUBSTRATES |
AU2005327546A AU2005327546A1 (en) | 2005-02-15 | 2005-11-14 | Composition and process for preparing chromium-zirconium coatings on metal substrates |
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US11/076,106 US20060180247A1 (en) | 2005-02-15 | 2005-02-15 | Process for preparing chromium conversion coatings for iron and iron alloys |
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US20060180247A1 true US20060180247A1 (en) | 2006-08-17 |
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US20070187001A1 (en) * | 2006-02-14 | 2007-08-16 | Kirk Kramer | Composition and Processes of a Dry-In-Place Trivalent Chromium Corrosion-Resistant Coating for Use on Metal Surfaces |
US20070221245A1 (en) * | 2006-03-23 | 2007-09-27 | Pawlik Michael J | Cleaning and polishing rusted iron-containing surfaces |
US20100132843A1 (en) * | 2006-05-10 | 2010-06-03 | Kirk Kramer | Trivalent Chromium-Containing Composition for Use in Corrosion Resistant Coatings on Metal Surfaces |
US20100300891A1 (en) * | 2009-05-29 | 2010-12-02 | Bulk Chemicals, Inc. | Method for Making and Using Chromium III Salts |
US8425692B2 (en) | 2010-05-27 | 2013-04-23 | Bulk Chemicals, Inc. | Process and composition for treating metal surfaces |
US10156016B2 (en) | 2013-03-15 | 2018-12-18 | Henkel Ag & Co. Kgaa | Trivalent chromium-containing composition for aluminum and aluminum alloys |
WO2019006614A1 (en) * | 2017-07-03 | 2019-01-10 | 深圳市宏昌发科技有限公司 | Passivator, metal workpiece and surface passivation process therefor |
US11008659B2 (en) | 2014-12-26 | 2021-05-18 | Dipsol Chemicals Co., Ltd. | Trivalent chromium chemical conversion liquid for zinc or zinc alloy bases and chemical conversion coating film |
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US20070187001A1 (en) * | 2006-02-14 | 2007-08-16 | Kirk Kramer | Composition and Processes of a Dry-In-Place Trivalent Chromium Corrosion-Resistant Coating for Use on Metal Surfaces |
US8092617B2 (en) | 2006-02-14 | 2012-01-10 | Henkel Ag & Co. Kgaa | Composition and processes of a dry-in-place trivalent chromium corrosion-resistant coating for use on metal surfaces |
US20070221245A1 (en) * | 2006-03-23 | 2007-09-27 | Pawlik Michael J | Cleaning and polishing rusted iron-containing surfaces |
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US20100132843A1 (en) * | 2006-05-10 | 2010-06-03 | Kirk Kramer | Trivalent Chromium-Containing Composition for Use in Corrosion Resistant Coatings on Metal Surfaces |
US9487866B2 (en) | 2006-05-10 | 2016-11-08 | Henkel Ag & Co. Kgaa | Trivalent chromium-containing composition for use in corrosion resistant coatings on metal surfaces |
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US8425692B2 (en) | 2010-05-27 | 2013-04-23 | Bulk Chemicals, Inc. | Process and composition for treating metal surfaces |
US10156016B2 (en) | 2013-03-15 | 2018-12-18 | Henkel Ag & Co. Kgaa | Trivalent chromium-containing composition for aluminum and aluminum alloys |
US11085115B2 (en) | 2013-03-15 | 2021-08-10 | Henkel Ag & Co. Kgaa | Trivalent chromium-containing composition for aluminum and aluminum alloys |
US11008659B2 (en) | 2014-12-26 | 2021-05-18 | Dipsol Chemicals Co., Ltd. | Trivalent chromium chemical conversion liquid for zinc or zinc alloy bases and chemical conversion coating film |
WO2019006614A1 (en) * | 2017-07-03 | 2019-01-10 | 深圳市宏昌发科技有限公司 | Passivator, metal workpiece and surface passivation process therefor |
Also Published As
Publication number | Publication date |
---|---|
CN101189073A (en) | 2008-05-28 |
CN101142340A (en) | 2008-03-12 |
CN101410550B (en) | 2011-12-07 |
CN101410550A (en) | 2009-04-15 |
CN101189073B (en) | 2011-05-18 |
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