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 PDF

Info

Publication number
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
Authority
US
United States
Prior art keywords
grams
water soluble
iron
aqueous solution
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US11/076,106
Other languages
English (en)
Inventor
Craig Matzdorf
William Nickerson
James Green
Andrew Schwartz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
US OF AMERICA NAVY THE, Secretary of
US Department of Navy
Original Assignee
US Department of Navy
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by US Department of Navy filed Critical US Department of Navy
Priority to US11/076,106 priority Critical patent/US20060180247A1/en
Assigned to U.S. OF AMERICA AS REPRESENTED BY THE SECRETARY OF THE NAVY, THE reassignment U.S. OF AMERICA AS REPRESENTED BY THE SECRETARY OF THE NAVY, THE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GREEN, JAMES L., MATZDORF, CRAIG A., NICKERSON, WILLIAM C., SCHWARTZ, ANDREW S.
Priority to CA2597630A priority patent/CA2597630C/en
Priority to AU2005327548A priority patent/AU2005327548A1/en
Priority to JP2007555078A priority patent/JP5060963B2/ja
Priority to CNA2005800483468A priority patent/CN101142340A/zh
Priority to JP2007555080A priority patent/JP5060964B2/ja
Priority to MX2007009801A priority patent/MX2007009801A/es
Priority to CN2005800483472A priority patent/CN101189073B/zh
Priority to DK05851687.3T priority patent/DK1848841T3/da
Priority to CA002598396A priority patent/CA2598396A1/en
Priority to MX2007009798A priority patent/MX2007009798A/es
Priority to MX2007009803A priority patent/MX2007009803A/es
Priority to BRPI0519981A priority patent/BRPI0519981B1/pt
Priority to DK05851727.7T priority patent/DK1863952T3/da
Priority to EP05851687A priority patent/EP1848841B1/en
Priority to PCT/US2005/041413 priority patent/WO2006088518A2/en
Priority to BRPI0519957A priority patent/BRPI0519957B1/pt
Priority to ES05851727T priority patent/ES2411429T3/es
Priority to KR1020077021138A priority patent/KR20080000564A/ko
Priority to ES05851687T priority patent/ES2413440T3/es
Priority to AU2005327546A priority patent/AU2005327546A1/en
Priority to KR1020077021173A priority patent/KR20080000565A/ko
Priority to JP2007555077A priority patent/JP2008530360A/ja
Priority to PCT/US2005/041414 priority patent/WO2006088519A2/en
Priority to KR1020077021175A priority patent/KR20070118085A/ko
Priority to CN2005800483449A priority patent/CN101410550B/zh
Priority to PCT/US2005/041587 priority patent/WO2006088521A2/en
Priority to CA002598397A priority patent/CA2598397A1/en
Priority to EP05851686A priority patent/EP1848840A2/en
Priority to AU2005327545A priority patent/AU2005327545A1/en
Priority to EP05851727A priority patent/EP1863952B1/en
Publication of US20060180247A1 publication Critical patent/US20060180247A1/en
Assigned to DSM PARTNERS, LTD. reassignment DSM PARTNERS, LTD. AMENDED AND RESTATED SECURITY AGREEMENT Assignors: METALAST INTERNATIONAL, LLC
Abandoned legal-status Critical Current

Links

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.
US11/076,106 2005-02-15 2005-02-15 Process for preparing chromium conversion coatings for iron and iron alloys Abandoned US20060180247A1 (en)

Priority Applications (31)

Application Number Priority Date Filing Date Title
US11/076,106 US20060180247A1 (en) 2005-02-15 2005-02-15 Process for preparing chromium conversion coatings for iron and iron alloys
EP05851727A EP1863952B1 (en) 2005-02-15 2005-11-14 Composition and process for preparing protective coatings on metal substrates
BRPI0519957A BRPI0519957B1 (pt) 2005-02-15 2005-11-14 processo para revestir substratos metálicos, e, composições para revestimento de substratos metálicos
KR1020077021138A KR20080000564A (ko) 2005-02-15 2005-11-14 금속 기판들 상에 보호성 코팅을 제공하기 위한 합성물 및방법
JP2007555078A JP5060963B2 (ja) 2005-02-15 2005-11-14 金属基質上へのクロミウム−ジルコニウムコーティング用組成物及びその調製方法
ES05851727T ES2411429T3 (es) 2005-02-15 2005-11-14 Composición y procedimiento para preparar revestimientos protectores sobre sustratos metálicos
JP2007555080A JP5060964B2 (ja) 2005-02-15 2005-11-14 金属基質の保護コーティング用組成物及び方法
MX2007009801A MX2007009801A (es) 2005-02-15 2005-11-14 Composicion y proceso para preparar revestimientos protectores sobre substratos de metal.
CN2005800483472A CN101189073B (zh) 2005-02-15 2005-11-14 用于在金属基底上制备铬-锆涂层的组合物和方法
AU2005327548A AU2005327548A1 (en) 2005-02-15 2005-11-14 Composition and process for preparing protective coatings on metal substrates
CA002598396A CA2598396A1 (en) 2005-02-15 2005-11-14 Composition and process for preparing chromium-zirconium coatings on metal substrates
MX2007009798A MX2007009798A (es) 2005-02-15 2005-11-14 Proceso para preparar revestimientos de conversion de cromo para hierro y aleaciones de hierro.
MX2007009803A MX2007009803A (es) 2005-02-15 2005-11-14 Composicion y proceso para preparar revestimientos de cromo-zirconio sobre substratos de metal.
BRPI0519981A BRPI0519981B1 (pt) 2005-02-15 2005-11-14 processo para revestir substratos metálicos, e, composições para uso em um processo para revestir de substratos metálicos
DK05851727.7T DK1863952T3 (da) 2005-02-15 2005-11-14 Sammensætning og fremgangsmåde til fremstilling af beskyttelsesovertræk på metalsubstrater
ES05851687T ES2413440T3 (es) 2005-02-15 2005-11-14 Composición y procedimiento para preparar revestimientos de cromo-circonio sobre sustratos metálicos
PCT/US2005/041413 WO2006088518A2 (en) 2005-02-15 2005-11-14 Process for preparing chromium conversion coatings for iron and iron alloys
CA2597630A CA2597630C (en) 2005-02-15 2005-11-14 Composition and process for preparing protective coatings on metal substrates
CNA2005800483468A CN101142340A (zh) 2005-02-15 2005-11-14 用于制备铁和铁合金用的铬转化涂层的方法
DK05851687.3T DK1848841T3 (da) 2005-02-15 2005-11-14 Sammensætning og fremgangsmåde til fremstilling af chrom-zirconium-coatings på metalsubstrater
EP05851687A EP1848841B1 (en) 2005-02-15 2005-11-14 Composition and process for preparing chromium-zirconium coatings on metal substrates
AU2005327546A AU2005327546A1 (en) 2005-02-15 2005-11-14 Composition and process for preparing chromium-zirconium coatings on metal substrates
KR1020077021173A KR20080000565A (ko) 2005-02-15 2005-11-14 금속 기판들 상에 크롬-지르코늄 코팅을 제공하기 위한합성물 및 방법
JP2007555077A JP2008530360A (ja) 2005-02-15 2005-11-14 鉄および鉄合金のためのクロミウム化成皮膜を調製する方法
PCT/US2005/041414 WO2006088519A2 (en) 2005-02-15 2005-11-14 Composition and process for preparing chromium-zirconium coatings on metal substrates
KR1020077021175A KR20070118085A (ko) 2005-02-15 2005-11-14 철 및 철 합금용 크롬 전환 코팅을 준비하기 위한 방법
CN2005800483449A CN101410550B (zh) 2005-02-15 2005-11-14 用于在金属基底上制备保护性涂层的组合物和方法
PCT/US2005/041587 WO2006088521A2 (en) 2005-02-15 2005-11-14 Composition and process for preparing protective coatings on metal substrates
CA002598397A CA2598397A1 (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
AU2005327545A AU2005327545A1 (en) 2005-02-15 2005-11-14 Process for preparing chromium conversion coatings for iron and iron alloys

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US11/076,106 US20060180247A1 (en) 2005-02-15 2005-02-15 Process for preparing chromium conversion coatings for iron and iron alloys

Publications (1)

Publication Number Publication Date
US20060180247A1 true US20060180247A1 (en) 2006-08-17

Family

ID=36814454

Family Applications (1)

Application Number Title Priority Date Filing Date
US11/076,106 Abandoned US20060180247A1 (en) 2005-02-15 2005-02-15 Process for preparing chromium conversion coatings for iron and iron alloys

Country Status (2)

Country Link
US (1) US20060180247A1 (zh)
CN (3) CN101189073B (zh)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (zh) * 2017-07-03 2019-01-10 深圳市宏昌发科技有限公司 钝化剂、金属工件及其表面钝化处理方法
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

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101748464B (zh) * 2008-12-18 2011-11-16 比亚迪股份有限公司 一种电解液及锆或锆合金表面微弧氧化方法
CN105518090B (zh) * 2013-08-28 2018-04-03 迪普索股份公司 3价铬化成被膜或无铬化成被膜的面涂剂用的摩擦调整剂及含有该摩擦调整剂的面涂剂
CN104862683A (zh) * 2015-04-08 2015-08-26 安徽豪鼎金属制品有限公司 一种丝胶钾皂金属表面处理剂
CN104862706A (zh) * 2015-04-08 2015-08-26 安徽豪鼎金属制品有限公司 一种环保水基金属表面处理剂
CN106222639B (zh) * 2016-08-17 2018-07-13 安徽红桥金属制造有限公司 一种弹簧钢铸件表面防锈预处理溶液
US10926237B2 (en) * 2018-02-02 2021-02-23 The Boeing Company Soluble corrosion resistant sol-gel
KR102500400B1 (ko) * 2018-03-29 2023-02-15 니혼 파커라이징 가부시키가이샤 표면 처리제, 그리고 표면 처리 피막을 갖는 알루미늄 또는 알루미늄 합금 재료 및 그 제조 방법
CN111394718B (zh) * 2020-03-04 2022-11-11 广东东明新材科技有限公司 钝化液及铜表面成膜处理方法
CN111809172A (zh) * 2020-07-22 2020-10-23 赤壁富祥盛科技有限公司 一种用于铝合金模板面层的钝化液
CN112626511A (zh) * 2020-11-27 2021-04-09 瑞声科技（南京）有限公司 钢片钝化工艺、钝化钢片以及均温板
CN114318315A (zh) * 2021-12-30 2022-04-12 中国石油大学(华东) 富锌三价铬转化膜制备溶液及该转化膜的制备方法

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5273837A (en) * 1992-12-23 1993-12-28 Corning Incorporated Solid electrolyte fuel cells
US5501914A (en) * 1993-09-01 1996-03-26 Mitsubishi Jukogyo Kabushiki Kaisha Solid oxide electrolyte fuel cell
US5518829A (en) * 1994-03-04 1996-05-21 Mitsubishi Jukogyo Kabushiki Kaisha Solid oxide electrolyte fuel cell having dimpled surfaces of a power generation film
US5942349A (en) * 1995-03-15 1999-08-24 Ceramic Fuel Cells Limited Fuel cell interconnect device
US6183829B1 (en) * 1997-11-07 2001-02-06 Rohm And Haas Company Process and apparatus for forming plastic sheet
US6280868B1 (en) * 1996-03-18 2001-08-28 Ceramic Fuel Cells Limited Electrical interconnect for a planar fuel cell
US6444340B1 (en) * 1997-09-05 2002-09-03 Ceramic Fuel Cells Limited Electrical conductivity in a fuel cell assembly
US6447620B1 (en) * 1998-06-01 2002-09-10 Henkel Corporation Water-based surface-treating agent for metallic material
US6461449B1 (en) * 1997-10-07 2002-10-08 Henkel Corporation Conversion coating zinciferous surfaces to resist blackening and white rust
US6492053B1 (en) * 1997-06-10 2002-12-10 Ceramic Fuel Cells Limited Planar fuel cell assembly
US20030230215A1 (en) * 2000-10-31 2003-12-18 Matzdorf Craig A. Pretreatment for aluminum and aluminum alloys

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07100873B2 (ja) * 1989-09-27 1995-11-01 日本パーカライジング株式会社 亜鉛系メッキ鋼板のクロメート塗布液
AU2002361689A1 (en) * 2002-01-04 2003-07-30 University Of Dayton Non-toxic corrosion protection pigments based on cobalt

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5273837A (en) * 1992-12-23 1993-12-28 Corning Incorporated Solid electrolyte fuel cells
US5501914A (en) * 1993-09-01 1996-03-26 Mitsubishi Jukogyo Kabushiki Kaisha Solid oxide electrolyte fuel cell
US5518829A (en) * 1994-03-04 1996-05-21 Mitsubishi Jukogyo Kabushiki Kaisha Solid oxide electrolyte fuel cell having dimpled surfaces of a power generation film
US5942349A (en) * 1995-03-15 1999-08-24 Ceramic Fuel Cells Limited Fuel cell interconnect device
US6280868B1 (en) * 1996-03-18 2001-08-28 Ceramic Fuel Cells Limited Electrical interconnect for a planar fuel cell
US6492053B1 (en) * 1997-06-10 2002-12-10 Ceramic Fuel Cells Limited Planar fuel cell assembly
US6444340B1 (en) * 1997-09-05 2002-09-03 Ceramic Fuel Cells Limited Electrical conductivity in a fuel cell assembly
US6461449B1 (en) * 1997-10-07 2002-10-08 Henkel Corporation Conversion coating zinciferous surfaces to resist blackening and white rust
US6183829B1 (en) * 1997-11-07 2001-02-06 Rohm And Haas Company Process and apparatus for forming plastic sheet
US6447620B1 (en) * 1998-06-01 2002-09-10 Henkel Corporation Water-based surface-treating agent for metallic material
US20030230215A1 (en) * 2000-10-31 2003-12-18 Matzdorf Craig A. Pretreatment for aluminum and aluminum alloys

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US7351295B2 (en) * 2006-03-23 2008-04-01 Pp6 Industries Ohio, Inc. 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
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
US8273190B2 (en) 2009-05-29 2012-09-25 Bulk Chemicals, Inc. Method for making and using chromium III salts
US8425693B2 (en) 2009-05-29 2013-04-23 Bulk Chemicals, Inc. Method for making and using chromium III salts
US8449695B2 (en) 2009-05-29 2013-05-28 Bulk Chemicals, Inc. Method for making and using chromium III salts
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
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 (zh) * 2017-07-03 2019-01-10 深圳市宏昌发科技有限公司 钝化剂、金属工件及其表面钝化处理方法

Also Published As

Publication number Publication date
CN101189073B (zh) 2011-05-18
CN101410550A (zh) 2009-04-15
CN101189073A (zh) 2008-05-28
CN101410550B (zh) 2011-12-07
CN101142340A (zh) 2008-03-12

Similar Documents

Publication Publication Date Title
US20060180247A1 (en) Process for preparing chromium conversion coatings for iron and iron alloys
US6511532B2 (en) Post-treatment for anodized aluminum
EP1853750B1 (en) Process for sealing phosphoric acid anodized aluminums
US6527841B2 (en) Post-treatment for metal coated substrates
EP1404894B1 (en) Corrosion resistant coatings for aluminum and aluminum alloys
US6521029B1 (en) Pretreatment for aluminum and aluminum alloys
US7811391B2 (en) Composition and process for preparing protective coatings on metal substrates
US6669764B1 (en) Pretreatment for aluminum and aluminum alloys
US20040187967A1 (en) Chemical conversion coating agent and surface-treated metal
EP1863952B1 (en) Composition and process for preparing protective coatings on metal substrates
US20100032060A1 (en) Process for preparing chromium conversion coatings for magnesium alloys
US20070099022A1 (en) Non-chromium post-treatment for aluminum coated steel
US20070095436A1 (en) Non-chromium coatings for aluminum
CA2598397A1 (en) Process for preparing chromium conversion coatings for iron and iron alloys
US20070095437A1 (en) Non-chromium conversion coatings for ferrous alloys

Legal Events

Date Code Title Description
AS Assignment

Owner name: U.S. OF AMERICA AS REPRESENTED BY THE SECRETARY OF

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MATZDORF, CRAIG A.;NICKERSON, WILLIAM C.;GREEN, JAMES L.;AND OTHERS;REEL/FRAME:016373/0671

Effective date: 20050126

STCB Information on status: application discontinuation

Free format text: ABANDONED -- AFTER EXAMINER'S ANSWER OR BOARD OF APPEALS DECISION

AS Assignment

Owner name: DSM PARTNERS, LTD., NEVADA

Free format text: AMENDED AND RESTATED SECURITY AGREEMENT;ASSIGNOR:METALAST INTERNATIONAL, LLC;REEL/FRAME:030649/0578

Effective date: 20090731