EP1853750A2 - Process for sealing phosphoric acid anodized aluminums - Google Patents

Process for sealing phosphoric acid anodized aluminums

Info

Publication number
EP1853750A2
EP1853750A2 EP05851693A EP05851693A EP1853750A2 EP 1853750 A2 EP1853750 A2 EP 1853750A2 EP 05851693 A EP05851693 A EP 05851693A EP 05851693 A EP05851693 A EP 05851693A EP 1853750 A2 EP1853750 A2 EP 1853750A2
Authority
EP
European Patent Office
Prior art keywords
grams
ranging
phosphoric acid
aqueous solution
water soluble
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.)
Granted
Application number
EP05851693A
Other languages
German (de)
French (fr)
Other versions
EP1853750A4 (en
EP1853750B1 (en
Inventor
Craig A. Matzdorf
William C. Nickerson, Jr.
Erin N. Beck
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.)
United States, AS REPRESENTED BY TH
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
Publication of EP1853750A2 publication Critical patent/EP1853750A2/en
Publication of EP1853750A4 publication Critical patent/EP1853750A4/en
Application granted granted Critical
Publication of EP1853750B1 publication Critical patent/EP1853750B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • C25D11/246—Chemical after-treatment for sealing layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment

Definitions

  • This invention relates to a process for depositing a film or coating onto aluminum and its alloys that have been phosphoric acid anodized.
  • the coating system comprises phosphoric acid anodize aluminums, a supplemental post-treatment or seal coating, optimally, an adhesive bond primer or other supplemental coatings.
  • Phosphoric acid anodized aluminum coatings are very porous and therefore have poor inherent corrosion resistance. These coatings do, however, have excellent adhesive properties. Accordingly these anodized coatings would benefit from a post-treatment or seal coating that enhances corrosion protection without adversely affecting the adhesion properties.
  • the performance characteristics of this invention allows the phosphoric acid anodized coatings to be used in unpainted applications which are currently unfeasible; to replace chromic acid anodize aluminum and FPL Etch, both of which contain chromates for corrosion-prone fatigue-sensitive applications; in all adhesive bonding applications where the and, in general use applications to reduce fatigue debit and coating weight compared to other general use anodize coatings.
  • This invention relates to a process for treating phosphoric acid anodized al ⁇ minum(s) to maintain and improve the corrosion-resistant properties. More specifically, this invention relates to the process of sealing phosphoric acid anodized aluminum and anodized aluminum alloys.
  • the trivalent chromium post-treatment (TCP) process comprises an acidic aqueous solution containing effective amounts of at least one water-soluble trivalent chromium compound, an alkali metal hexafluorozirconate, at least one alkali metal tetrafluoroborate and/or hexafluorosilicate, at least one divalent zinc compound, and effective amounts of water-soluble thickeners and/or water-soluble surfactants.
  • Anodized aluminum(s) are generally sealed or post-treated after anodizing by processes employing a variety of sealing processes and compositions.
  • Current high- performance post treatments or sealers for anodized aluminum are based on hexavalent chromium chemistry. Hexavalent chromium is highly toxic and a known carcinogen. As a result, the solutions used to deposit these protective coatings and the coating per se are toxic. These films or coatings do, however, yield good adhesion and improved corrosion resistance to the anodized aluminum.
  • seal coatings are deposited onto the anodized coating at elevated temperatures and are usually applied by immersion or spray processes. Post treatments can be required by the military and by commercial specifications that govern each coating being treated.
  • hexavalent chromium-treatments are becoming more expensive as regulations tighten. Costs may become prohibitive with future restrictions imposed by the EPA.
  • hexavalent chromium-treatments are outstanding in their technical performance in that they provide enhanced corrosion protection and adhesion bonding e.g. with coatings such as paint at a low application cost, from a life-cycle cost, environmental, and OSH perspective, hexavalent chromium coatings are detrimental to both people and the environment.
  • adhesive bonding phosphoric acid anodize is being implemented as an alternative to chromic acid anodize. Phosphoric acid anodize coatings provide excellent adhesive bonding performance, but fail to adequately protect the base aluminum from corrosion.
  • anodize sealers are typically applied to various other anodize coatings to boost corrosion performance, they are generally not applied to phosphoric acid anodize coatings because the adhesive bonding performance is significantly reduced.
  • the corrosion protection of a phosphoric acid anodized coating is provided by chromated bond primers or general use primers.
  • Phosphoric acid anodize coatings are characteristically columnar and porous, thus promoting excellent adhesive bonding performance.
  • the columnar, porous structure also promotes corrosion making ⁇ hds ⁇ hM ⁇ &Md anotf ⁇ zti (T ⁇ Mags particularly difficult to protect against corrosion.
  • phosphoric acid anodized "honeycomb" core commonly used in military aircraft, corrodes quickly in service when its protective coating is damaged and would greatly benefit from a corrosion protective sealer that does not adversely impact the adhesive bonding characteristics of the anodize coating.
  • This invention relates to a process of post-treating or sealing phosphoric acid anodized aluminum and its alloys at ambient temperatures or higher e.g. ranging up to about 200 0 F. More specifically, this invention relates to post-treating phosphoric acid anodized aluminum and its alloys to improve the corrosion-resistance and maintain adhesion bonding properties e.g. paint adhesion and the like.
  • the trivalent chromium post-treatment (TCP) composition of this invention comprises an acidic aqueous solution having a pH ranging from about 2.5 to 5.5 and preferably 2.5 to 4.5 or 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, about 0.0 to 12 or 0.001 to 12 grams of at least one fluorocompound selected from the group consisting of an alkali metal tetrafluoroborate, an alkali metal hexafluorosilicate and various combinations or mixtures thereof in any ratio, 0.001 to 10 grams of a water soluble divalent zinc compound, from about 0 to 10 grams and preferable 0 to 2.0 grams of at least one water-soluble thickener, and from 0 to 10 and preferably 0 to 2.0 grams of at least one water-soluble non-ionic, cationic or anionic surfactant or
  • Fig. 1 is a photo of phosphoric acid anodized aluminum, 2024-T3 with no post treatment after exposure to 24 hours (1 day) of ASTM-B 117 neutral salt fog test.
  • Fig. " ⁇ Ts 1 a photo of phosphoric acid anodized 2024-T3 post treated with the composition of Example 5 (10 minute immersion at about 75 0 F) after exposure to 96 hours (4 days) of ASTM-B 117 neutral salt fog test.
  • Fig.3 is a photo of a phosphoric acid anodized 2024-T3 post treated with the composition of Example 6 (10 minute immersion at about 75 0 F) after exposure to 96 hours (4 days) of ASTM-B 117 neutral salt fog test.
  • Fig. 4 is a photo of phosphoric acid anodized 2024-T3 post treated with the composition of Example 5 (10 minutes at 100 0 F) after exposure to 1000 hours (42 days) of ASTM-B 117 neutral salt fog test.
  • Fig. 5 is a photo of a phosphoric acid anodized 2024-T3 post treated with the composition of Example 7 (10 minutes at 100 0 F) after exposure to 1000 hours (42 days) of ASTM-B 117 neutral salt fog test.
  • Fig. 6 is a photo of a phosphoric acid anodized 2024-T3 post treated with the composition of Example 5 (40 minutes at ambient (75 0 F)) after exposure to 1000 hours (42 days) of ASTM-B 117 neutral salt fog test.
  • Fig. 7 is a photo of a phosphoric acid anodized 2024-T3 post treated with the composition of Example 7 (40 minutes at ambient (75 0 F)) after exposure to 1000 hours (42 days) of ASTM-B 117 neutral salt fog test.
  • Fig. 8 is a photo of a phosphoric acid anodized 2024-T3 post treated with the composition of Example 5 (5 minutes at 150 0 F) after exposure to 1000 hours (42 days) of ASTM-B 117 neutral salt fog test.
  • Fig. 9 is a photo of a phosphoric acid anodized 2024-T3 post treated with the composition of Example 6 (5 minutes at 150 0 F ) after exposure to 1000 hours (42 days) of ASTM-B 117 neutral salt fog test.
  • 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 sealing phosphoric acid anodized aluminum and its alloys to maintain its adhesion bonding and to substantially improve the corrosion-resistance properties of the anodized aluminum(s).
  • the process preferably comprises the use of an acidic solution comprising from about 0.01 to 22 grams and preferably from about 4.0 to 8.0 grams e.g. 6.0 grams of at least one water soluble trivalent chromium compound e.g. chromium sulfate, about 0.01 to 12 grams and preferably about 6.0 to 10 grams e.g.
  • a 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. Moreover, the addition of thickeners, aids in proper film formation during large area applications and mitigates the diluent effect of rinse water remaining on the substrate during processing from previous steps.
  • This additive yields films that have no streaks and have better coloration and corrosion prl ⁇ tec1do ⁇ /"Tfil ⁇ ter- ⁇ luBf ⁇ 'tffickeners such as the cellulose compounds are known, and can be present in the acidic aqueous solution in amounts ranging from about 0.0 to 10 grams and preferably from 0.0 to 2.0 grams and more preferably from 0.5 to 1.5 e.g., 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 0.0 to 2.0 grams and more preferably from 0.5 to 1.5 grams e.g. 1.0 grams per liter of the acidic solution.
  • These water soluble surfactants or wetting agents are known in the prior art and are selected from the group consisting of non-ionic, cationic and anionic surfactants.
  • the trivalent chromium is added 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 can be prepared in solution in the form of Cr 2 (SCXf) 3 , (NH 4 )Cr(SO,! ⁇ or KCr 2 (SO 4 ) 2 and any mixtures or combination of these compounds.
  • the aluminum substrates are either phosphoric acid anodized aluminum or anodized aluminum alloys containing about 60% or more by weight of aluminum.
  • a preferred example of trivalent chromium concentration is within the range of about 4.0 to 8.0 grams or 6.0 grams per liter of the aqueous solution. It has been found that particularly good results are obtained when the trivalent chromium compound is present in solution in these preferred ranges.
  • the preferred metal fluorozirconate addition to the acidic solution ranges from about 6.0 to 10 grams or 8.0 grams per liter of solution.
  • acid anodized aluminum can be carried out at low temperatures e.g. about ambient or room temperature or at temperatures ranging up to about 200 0 F.
  • the seal coating may be air dried by any of the methods known in the art, for example, oven drying, forced air drying, exposure to infra-red lamps, and the like.
  • phosphoric acid anodized aluminum and anodized aluminum alloys include aluminum and its alloys phosphoric acid anodized by methods known in the art.
  • the alkali metal tetrafLuoroborates and/or hexafluorosilicates can be added to the acidic solution in amounts as low as 0.001 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.
  • about 1 to 10 weight percent e.g. about 3% of the fluoroborate salt can be added based on the weight of the fluorozirconate salt.
  • a specific example comprises about 8.0 grams per liter of potassium hexafluorozirconate, about 6.0 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 1.2 grams per liter of potassium tetrafluoroborate and/or hexafluorosilicate.
  • An important result of the addition of the stabilizing additives i.e. fluoroborates and/or fluorosilicates is that the solution is stable while the pH is maintained between about 2.5 and 5.5.
  • the pretreatment solutions may require small amounts of a dilute acid or base to maintain the pH in the range of about 2.5 to 5.5 or lower e.g. from about 3.25 to 3.5.
  • the composition or acid solution can also contain zinc compounds to further improve the corrosion protection of the phosphoric acid anodized coatings compared to compositions that do not contain divalent zinc compounds.
  • the components of the solution are mixed together in water and can be used with no further chemical manipulation.
  • the divalent zinc can be supplied by any chemical compound that dissolves in water at the required concentrations ranging from 0.001 to 10 grams and is compatible with the other components in the solution.
  • Compounds that are particularly preferred 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.
  • a stable acidic aqueous solution having a pH ranging from about 3.45 to 4.0 for post-treating phosphoric acid anodized aluminum and aluminum alloys to provide a corrosion-resistant and a color recognized coating thereon which 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 zinc sulfate.
  • a stable acidic aqueous solution for post-treating phosphoric acid anodized aluminum and aluminum alloys to form a corrosion-resistant coating thereon which comprises, per liter of solution, about 3.0 grams of trivalent chromium sulfate basic, about 4.0 grams of potassium hexafluorozirconate, and about 0.12 grams of potassium tetrafluoroborate.
  • a stable acidic aqueous solution for post-treating phosphoric acid anodized aluminum and aluminum alloys to provide a corrosion-resistant and a color recognized coating thereon which 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.
  • Table 1 shows the corrosion ratings of three Examples for post-treating phosphoric acid anodized aluminum alloys of this invention in comparison to the composition of Example 2 coatings.
  • Example 3 (TCP5B3Z4) and Example 1 (TCP5PZ2) on average had higher ratings.
  • Example 4 To Example 4, add 1.0 grams per liter of zinc sulfate during initial mixing. Solution is ready to use.
  • Example 5 To Example 5, add 2.0 grams per liter of zinc sulfate during initial mixing.
  • Post treatment coatings were applied to anodized aluminum as follows.
  • the phosphoric acid anodize process per ASTM D 3933, "Standard Practice for Preparation of Aluminum Surfaces for Structural Adhesives Bonding (Phosphoric Acid Anodizing)," was followed throughout.
  • anodizing 3" by 10" by 0.32" aluminum panels of 2024-T3 aluminum alloys by the Phosphoric Acid Anodize process the panels were rinsed thoroughly two times in deionized water.
  • the panels were immersed into a solution of either Example 6 or 7 for 10 minutes at ambient conditions. The immersion was immediately followed by two deionized water rinses.
  • the panels were air-dried at ambient conditions before being subjected to neutral salt fog per ASTM B 117.
  • the coupons were held in a rack at 15 degrees for the duration of the test"
  • Control coupons of pitiospt ⁇ c acid anodized (PAA) not sealed were tested alongside the subject coatings.
  • Fig's.2 and 3 show the performance of post treatments from the compositions of Examples 5 and 6.
  • Fig. 1 shows an unsealed PAA panel after exposure to ASTM B 117 neutral salt fog.
  • the post treatments of Fig's.2. and 3 provide improved corrosion resistance compared to the no post-treatment coating of Fig. 1.
  • Test specimens were anodized as in Example 8.
  • the compositions (solutions) from Examples 5 and 7 were heated to 100° Fahrenheit and the panels were immersed for a total of 10 minutes.
  • Fig's. 4 and 5 show corrosion performance of these coatings after 1000 hours of neutral salt fog per ASTM B 117. It is evident that the composition of example 7 is an improvement compared to the composition of Example 5.
  • Test specimens were anodized as in Example 8.
  • the compositions (solutions) from Examples 5 and 7 were kept at ambient conditions, about 75° Fahrenheit, and the panels were immersed for a total of 40 minutes.
  • Fig's. 6 and 7 (photos) show the improved corrosion resistance of these coating after 1000 hours of neutral salt fog per ASTM B 117. 1 EXAMPLE I l
  • Test specimens were anodized as in Example 8.
  • the compositions (solutions) from Examples 5 and 6 were heated to 150° Fahrenheit, and the panels were immersed for a total of 5 minutes.
  • Fig's. 7 and 8 (photos) show the corrosion resistance of these coatings after 1000 hours of neutral salt fog per ASTM B 117.
  • Table 2 compares the corrosion resistance results of the Examples based on numerical ratings from ASTM D 1654. hi the ASTM rating method, the best possible score is 10, meaning substantially no corrosion is evident on the test panel. Ratings decrease to 1, which represents substantially 100% corrosion of the panel surface. From the data in Table 2, it is evident that the process of this invention is an improvement over previous processes used for post treating or sealing phosphoric acid anodized aluminum and its alloys.
  • the water soluble surfactants or wetting agents can be added to the trivalent chromium solutions in amounts ranging from about 0 to 10 grams per liter and preferably 0.5 to about 1.5 grams per liter of the trivalent chromium solution.
  • 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 coated substrate.
  • the surfactants include at least one water soluble compound selected from the group consisting of the non-ionic, anionic, and cationic surfactants.
  • Some known water soluble surfactants having the solubility at the required concentrations include the monocarboxyl imidoazoline, alkyl sulfate sodium salts (DUPONOL®), tridecyloxy poly(alkyleneoxy ethanol) ethoxylated or propoxylated alkyl phenol (IGEPAL®), alkyl sulfonamides, alkaryl sulfonates, palmitic alkanol amides (CENTROL®), octylphenyl polyethoxy ethanol (TRITON®), sorbitan monopahnitate (SPAN®), dodecylphenyl polyethylene glycol ether e.g.
  • TERGITROL® alkyl pyrrolidone, polyalkoxylated fatty acid esters, alkylbenzene sulfonates and mixtures thereof.
  • Other known water soluble surfactants include the alkyl phenol alkyloxylates, ' preferably me n ⁇ nylphenol effiyloxylates, and the various anionic surfactants, having at least one sulfonate substituent in the phenyl ring, and the adducts of ethylene oxide with fatty amines.
  • Other known water soluble compounds are found in "Surfactants and Detersive Systems", published by John Wiley & Sops in Kirk-Othmer's Encyclopedia of Chemical Technology, 3 rd Ed.
  • thickening agents When large surfaces do not permit immersion or where vertical surfaces are to be sprayed, thickening agents are added to retain the aqueous solution on the surface for sufficient contact tune.
  • the thickeners employed are known inorganic and organic water soluble thickeners which can be added to the trivalent chromium solutions in effective amounts e.g. a sufficient concentration 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, methyl cellulose and mixtures thereof.
  • Some of the less preferred thickeners include the water soluble inorganic thickeners such as colloidal silica, clays such as bentonite, starches, gum arabic, tragacanth, agar and various combinations.
  • the solution can be applied by immersion, spray or wipe-on techniques.
  • the solution also can be used at elevated temperatures up to 65°C and optimally applied by immersion to further improve the corrosion resistance of phosphoric acid anodize coatings.
  • Solution dwell time is about 1 to 60 minutes, depending on the solution temperature and concentration of the solution. After dwelling, the remaining solution is then thoroughly rinsed from the substrate with tap or deionized water. No additional chemical manipulations of the deposited film are necessary for excellent performance.
  • an application of a strong oxidizing solution can yield a film with improved corrosion resistance. The additional corrosion resistance is presumed to be due to the hexavalent chromium formed in the film from the trivalent chromium.
  • the aqueous sealer composition 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 the ability of this protective seal coating to provide the phosphoric acid anodized coatings with corrosion resistance better or at least equivalent to other known sealed anodic coatings produced with sulfuric, chromic, boric- sulfuric, or other known compositions.
  • This capability has not been available before and offers new potential applications for phosphoric acid anodized in corrosive environments that were not previously possible.
  • Phosphoric acid anodized aluminums have a major advantage over these other coatings in that its coating weights are typically 10 to 50 times lower. This yields significant weight savings and lower fatigue debit to structural aluminum alloys.
  • this invention has the ability to enhance the performance of phosphoric acid anodize coatings currently being implemented as an adhesive bonding alternative to chromic acid anodizing.
  • Phosphoric acid anodize coatings that have not been post treated are known to have inferior corrosion resistance, but are known also to have excellent bonding characteristics.
  • This invention increases the corrosion performance of the anodized aluminums, while mamtaining the adhesive bonding strength of the coatings.
  • solubility and water soluble mean water solubility of the chemical compounds used in the solutions of this invention at least at the concentrations set-forth herein. While “ ItSs invention nas"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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Glass Compositions (AREA)
  • Sealing Material Composition (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Lubricants (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

Process of seal coating phosphoric acid anodized aluminum and aluminum alloys to improve the corrosion resistance and maintain the adhesive bonding properties. The process comprises post-treating phosphoric acid anodized aluminum and its alloys with an acidic aqueous solution comprising, per liter of 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, about 0.0 to 12 grams of at least one alkali metal tetrafluorosilicate and/or an alkali metal hexafluoroborate, from about 0.001 to 10 grams of at least one water soluble divalent zinc compound and from 0.0 to 10 grams of a water soluble thickener and/or water soluble surfactant.

Description

PROCESS FOR SEALING PHOSPHORIC ACID ANODIZED ALUMINUMS
ORIGIN OF INVENTION
The invention described herein was made by employeφ) 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.
BACKGROUND OF THE INVENTION FIELD OF THE INVENTION
This invention relates to a process for depositing a film or coating onto aluminum and its alloys that have been phosphoric acid anodized. The coating system comprises phosphoric acid anodize aluminums, a supplemental post-treatment or seal coating, optimally, an adhesive bond primer or other supplemental coatings. Phosphoric acid anodized aluminum coatings are very porous and therefore have poor inherent corrosion resistance. These coatings do, however, have excellent adhesive properties. Accordingly these anodized coatings would benefit from a post-treatment or seal coating that enhances corrosion protection without adversely affecting the adhesion properties. The performance characteristics of this invention allows the phosphoric acid anodized coatings to be used in unpainted applications which are currently unfeasible; to replace chromic acid anodize aluminum and FPL Etch, both of which contain chromates for corrosion-prone fatigue-sensitive applications; in all adhesive bonding applications where the and, in general use applications to reduce fatigue debit and coating weight compared to other general use anodize coatings.
This invention relates to a process for treating phosphoric acid anodized alυminum(s) to maintain and improve the corrosion-resistant properties. More specifically, this invention relates to the process of sealing phosphoric acid anodized aluminum and anodized aluminum alloys. The trivalent chromium post-treatment (TCP) process comprises an acidic aqueous solution containing effective amounts of at least one water-soluble trivalent chromium compound, an alkali metal hexafluorozirconate, at least one alkali metal tetrafluoroborate and/or hexafluorosilicate, at least one divalent zinc compound, and effective amounts of water-soluble thickeners and/or water-soluble surfactants.
Anodized aluminum(s) are generally sealed or post-treated after anodizing by processes employing a variety of sealing processes and compositions. Current high- performance post treatments or sealers for anodized aluminum are based on hexavalent chromium chemistry. Hexavalent chromium is highly toxic and a known carcinogen. As a result, the solutions used to deposit these protective coatings and the coating per se are toxic. These films or coatings do, however, yield good adhesion and improved corrosion resistance to the anodized aluminum. Typically, seal coatings are deposited onto the anodized coating at elevated temperatures and are usually applied by immersion or spray processes. Post treatments can be required by the military and by commercial specifications that govern each coating being treated. As such, there is not a unique "post treatment" specification for all anodize aluminums like there is for "conversion coating" aluminum. executive orders, and local occupational, safety, and health (OSH) regulations are driving the military and commercial users in the search for hexavalent chromium-firee treatments. In the case of anodized aluminum, the anodize film and base metal are relatively non-toxic. With the addition of the required hexavalent chromium-treatment, these coatings become toxic. While some other compositions used for coating anodized aluminum may not contain hexavalent chromium, their technical performance is inferior to the hexavalent chromium-based coatings. Tn addition, the use of hexavalent chromium-treatments is becoming more expensive as regulations tighten. Costs may become prohibitive with future restrictions imposed by the EPA. Thus, while existing hexavalent chromium-treatments are outstanding in their technical performance in that they provide enhanced corrosion protection and adhesion bonding e.g. with coatings such as paint at a low application cost, from a life-cycle cost, environmental, and OSH perspective, hexavalent chromium coatings are detrimental to both people and the environment. In regard to adhesive bonding, phosphoric acid anodize is being implemented as an alternative to chromic acid anodize. Phosphoric acid anodize coatings provide excellent adhesive bonding performance, but fail to adequately protect the base aluminum from corrosion. While anodize sealers are typically applied to various other anodize coatings to boost corrosion performance, they are generally not applied to phosphoric acid anodize coatings because the adhesive bonding performance is significantly reduced. As a result, the corrosion protection of a phosphoric acid anodized coating is provided by chromated bond primers or general use primers. Phosphoric acid anodize coatings are characteristically columnar and porous, thus promoting excellent adhesive bonding performance. However, the columnar, porous structure also promotes corrosion making ^hdsφhMϊ&Md anotfϊzti (TόMags particularly difficult to protect against corrosion. For example, phosphoric acid anodized "honeycomb" core, commonly used in military aircraft, corrodes quickly in service when its protective coating is damaged and would greatly benefit from a corrosion protective sealer that does not adversely impact the adhesive bonding characteristics of the anodize coating.
SUMMARY OF THE INVENTION
This invention relates to a process of post-treating or sealing phosphoric acid anodized aluminum and its alloys at ambient temperatures or higher e.g. ranging up to about 2000F. More specifically, this invention relates to post-treating phosphoric acid anodized aluminum and its alloys to improve the corrosion-resistance and maintain adhesion bonding properties e.g. paint adhesion and the like. The trivalent chromium post-treatment (TCP) composition of this invention comprises an acidic aqueous solution having a pH ranging from about 2.5 to 5.5 and preferably 2.5 to 4.5 or 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, about 0.0 to 12 or 0.001 to 12 grams of at least one fluorocompound selected from the group consisting of an alkali metal tetrafluoroborate, an alkali metal hexafluorosilicate and various combinations or mixtures thereof in any ratio, 0.001 to 10 grams of a water soluble divalent zinc compound, from about 0 to 10 grams and preferable 0 to 2.0 grams of at least one water-soluble thickener, and from 0 to 10 and preferably 0 to 2.0 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 atrivalent chromium compound, an alkali metal hexafluorozirconate, and a tetrafluoroborate and/or hexafluorosilicate for treating phosphoric acid anodized aluminum and its alloys to maintain its adhesion and improve its corrosion-resistance characteristics.
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 contains effective amounts of a trivalent chromium salt and a hexafluorozirconate for sealing phosphoric acid anodized aluminum and its anodized alloys. 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 containing a trivalent chromium salt and a hexafluorozirconate for treating or sealing phosphoric acid anodized aluminum and its alloys at about room temperature and higher wherein said acidic solution contains substantially no hexavalent chromium. These and other objects of the invention will become apparent by reference to the detailed description when considered in conjunction with the accompanying Figs. 1-9 (photos).
DESCRIPTION OF THE DRAWINGS
Fig. 1 is a photo of phosphoric acid anodized aluminum, 2024-T3 with no post treatment after exposure to 24 hours (1 day) of ASTM-B 117 neutral salt fog test. Fig. "ϊ Ts1 a photo of phosphoric acid anodized 2024-T3 post treated with the composition of Example 5 (10 minute immersion at about 750F) after exposure to 96 hours (4 days) of ASTM-B 117 neutral salt fog test.
Fig.3 is a photo of a phosphoric acid anodized 2024-T3 post treated with the composition of Example 6 (10 minute immersion at about 750F) after exposure to 96 hours (4 days) of ASTM-B 117 neutral salt fog test.
Fig. 4 is a photo of phosphoric acid anodized 2024-T3 post treated with the composition of Example 5 (10 minutes at 1000F) after exposure to 1000 hours (42 days) of ASTM-B 117 neutral salt fog test. Fig. 5 is a photo of a phosphoric acid anodized 2024-T3 post treated with the composition of Example 7 (10 minutes at 1000F) after exposure to 1000 hours (42 days) of ASTM-B 117 neutral salt fog test.
Fig. 6 is a photo of a phosphoric acid anodized 2024-T3 post treated with the composition of Example 5 (40 minutes at ambient (750F)) after exposure to 1000 hours (42 days) of ASTM-B 117 neutral salt fog test.
Fig. 7 is a photo of a phosphoric acid anodized 2024-T3 post treated with the composition of Example 7 (40 minutes at ambient (750F)) after exposure to 1000 hours (42 days) of ASTM-B 117 neutral salt fog test.
Fig. 8 is a photo of a phosphoric acid anodized 2024-T3 post treated with the composition of Example 5 (5 minutes at 1500F) after exposure to 1000 hours (42 days) of ASTM-B 117 neutral salt fog test.
Fig. 9 is a photo of a phosphoric acid anodized 2024-T3 post treated with the composition of Example 6 (5 minutes at 1500F ) after exposure to 1000 hours (42 days) of ASTM-B 117 neutral salt fog test. DETAILED DESCRIPTlbK DFTHE INVENTION
More specifically, 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 sealing phosphoric acid anodized aluminum and its alloys to maintain its adhesion bonding and to substantially improve the corrosion-resistance properties of the anodized aluminum(s). The process preferably comprises the use of an acidic solution comprising from about 0.01 to 22 grams and preferably from about 4.0 to 8.0 grams e.g. 6.0 grams of at least one water soluble trivalent chromium compound e.g. chromium sulfate, about 0.01 to 12 grams and preferably about 6.0 to 10 grams e.g. 8.0 grams of at least one alkali metal hexafluorozirconate, about 0.0 to 12 or about 0.001 to 12 grams and preferably about 0.12 to 1.2 grams e.g. 0.24 to 0.36 grams of at least one fluorocompound selected from the group consisting of alkali metal tetrafiuoroborates, alkali metal hexafluorosilicates and various mixtures or combinations thereof in any ratio, and from about 0.Θ01 to 10 grams and preferably 0.1 to 5.0 or 1.0 to 2.0 grams of at least one divalent zinc compound such as zinc sulfate.
In some processes, depending on the physical characteristics of the anodized aluminum e.g. the physical size of the anodized substrate, a 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. Moreover, the addition of thickeners, aids in proper film formation during large area applications and mitigates the diluent effect of rinse water remaining on the substrate during processing from previous steps. This additive yields films that have no streaks and have better coloration and corrosion prlδtec1do¥/"Tfil^ter-^luBfø'tffickeners such as the cellulose compounds are known, and can be present in the acidic aqueous solution in amounts ranging from about 0.0 to 10 grams and preferably from 0.0 to 2.0 grams and more preferably from 0.5 to 1.5 e.g., about 1.0 gram per liter of the aqueous solution. Depending on the characteristics of the anodized aluminum, 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 0.0 to 2.0 grams and more preferably from 0.5 to 1.5 grams e.g. 1.0 grams per liter of the acidic solution. These water soluble surfactants or wetting agents are known in the prior art and are selected from the group consisting of non-ionic, cationic and anionic surfactants.
The trivalent chromium is added 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 can be prepared in solution in the form of Cr2(SCXf)3, (NH4)Cr(SO,!^ or KCr2(SO4)2 and any mixtures or combination of these compounds. The aluminum substrates are either phosphoric acid anodized aluminum or anodized aluminum alloys containing about 60% or more by weight of aluminum. A preferred example of trivalent chromium concentration is within the range of about 4.0 to 8.0 grams or 6.0 grams per liter of the aqueous solution. It has been found that particularly good results are obtained when the trivalent chromium compound is present in solution in these preferred ranges. The preferred metal fluorozirconate addition to the acidic solution ranges from about 6.0 to 10 grams or 8.0 grams per liter of solution. acid anodized aluminum can be carried out at low temperatures e.g. about ambient or room temperature or at temperatures ranging up to about 2000F. Room temperature treatment is preferred in that this eliminates the necessity for heating equipment The seal coating may be air dried by any of the methods known in the art, for example, oven drying, forced air drying, exposure to infra-red lamps, and the like. For purposes of this invention, the terms phosphoric acid anodized aluminum and anodized aluminum alloys include aluminum and its alloys phosphoric acid anodized by methods known in the art.
In some treatments, the alkali metal tetrafLuoroborates and/or hexafluorosilicates can be added to the acidic solution in amounts as low as 0.001 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. For example, an alternative is to add about 0.01 to 100 weight percent of the fluoroborate salt based on the weight of the fluorozirconate salt.
Preferably, about 1 to 10 weight percent e.g. about 3% of the fluoroborate salt can be added based on the weight of the fluorozirconate salt. A specific example comprises about 8.0 grams per liter of potassium hexafluorozirconate, about 6.0 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 1.2 grams per liter of potassium tetrafluoroborate and/or hexafluorosilicate. An important result of the addition of the stabilizing additives i.e. 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 cases the pretreatment solutions may require small amounts of a dilute acid or base to maintain the pH in the range of about 2.5 to 5.5 or lower e.g. from about 3.25 to 3.5.. The composition or acid solution can also contain zinc compounds to further improve the corrosion protection of the phosphoric acid anodized coatings compared to compositions that do not contain divalent zinc compounds. The components of the solution are mixed together in water and can be used with no further chemical manipulation. The divalent zinc can be supplied by any chemical compound that dissolves in water at the required concentrations ranging from 0.001 to 10 grams and is compatible with the other components in the solution. Compounds that are particularly preferred 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 following Examples illustrate the stable seal-coating solutions of this invention, and the method of using the solutions in maintaining the adhesion properties while improving the corrosion-resistance of phosphoric acid anodized aluminum and its alloys.
EXAMPLE 1 TCP5PZ2
A stable acidic aqueous solution having a pH ranging from about 3.45 to 4.0 for post-treating phosphoric acid anodized aluminum and aluminum alloys to provide a corrosion-resistant and a color recognized coating thereon which 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 zinc sulfate. EXAMPLE 2 TCP5B3
A stable acidic aqueous solution for post-treating phosphoric acid anodized aluminum and aluminum alloys to form a corrosion-resistant coating thereon which comprises, per liter of solution, about 3.0 grams of trivalent chromium sulfate basic, about 4.0 grams of potassium hexafluorozirconate, and about 0.12 grams of potassium tetrafluoroborate.
EXAMPLE 3
TCP5B3Z4
A stable acidic aqueous solution for post-treating phosphoric acid anodized aluminum and aluminum alloys to provide a corrosion-resistant and a color recognized coating thereon which 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.
Table 1 shows the corrosion ratings of three Examples for post-treating phosphoric acid anodized aluminum alloys of this invention in comparison to the composition of Example 2 coatings. Example 3 (TCP5B3Z4) and Example 1 (TCP5PZ2) on average had higher ratings. TABLE l Corrosion Resistance of Phosphoric Acid Anodize with Sealer on 2024-T3 Aluminum
Alloy After 1,000 Hours of Exposure to ASTM B 117 Neutral Salt Spray Immersion conditions
Note: Eac rat ng s t e average o 3 ent ca y coate an expose pane s
Corrosion ratings per ASTM D 1654
EXAMPLE 4
Add 3.0 grams per liter of chromium III sulfate basic and 4.0 grams per liter of potassium hexafluorozirconate to specific volume of deionized water. Maintain pH between 3.25 and 3.60 for 14 days using dilute potassium hydroxide or dilute sulfuric acid. After 14 days, adjust pH to 3.90 +/-0.05 and let sit overnight. Solution is ready to use.
EXAMPLE 5
Add 3.0 grams per liter of chromium HI sulfate basic, 4.0 grams per liter of potassium hexafluorozirconate, and 0.12 grams per liter potassium tetrafluoroborate to Let solution stand for approximately 10 days, or until pH rises to between 3.75 and 4.00. Solution is ready to use.
EXAMPLE 6
To Example 4, add 1.0 grams per liter of zinc sulfate during initial mixing. Solution is ready to use.
EXAMPLE ?
To Example 5, add 2.0 grams per liter of zinc sulfate during initial mixing.
Solution is ready to use.
EXAMPLE S
Post treatment coatings were applied to anodized aluminum as follows. The phosphoric acid anodize process per ASTM D 3933, "Standard Practice for Preparation of Aluminum Surfaces for Structural Adhesives Bonding (Phosphoric Acid Anodizing)," was followed throughout. Immediately after anodizing 3" by 10" by 0.32" aluminum panels of 2024-T3 aluminum alloys by the Phosphoric Acid Anodize process, the panels were rinsed thoroughly two times in deionized water. Immediately after rinsing, the panels were immersed into a solution of either Example 6 or 7 for 10 minutes at ambient conditions. The immersion was immediately followed by two deionized water rinses. The panels were air-dried at ambient conditions before being subjected to neutral salt fog per ASTM B 117. The coupons were held in a rack at 15 degrees for the duration of the test" Control coupons of pitiosptϊόπc acid anodized (PAA) not sealed were tested alongside the subject coatings.
Fig's.2 and 3 (photos) show the performance of post treatments from the compositions of Examples 5 and 6. Fig. 1 (photo) shows an unsealed PAA panel after exposure to ASTM B 117 neutral salt fog. The post treatments of Fig's.2. and 3 provide improved corrosion resistance compared to the no post-treatment coating of Fig. 1.
EXAMPLE 9
Test specimens were anodized as in Example 8. In this example, the compositions (solutions) from Examples 5 and 7 were heated to 100° Fahrenheit and the panels were immersed for a total of 10 minutes. Fig's. 4 and 5 (photos) show corrosion performance of these coatings after 1000 hours of neutral salt fog per ASTM B 117. It is evident that the composition of example 7 is an improvement compared to the composition of Example 5.
EXAMPLE 10
Test specimens were anodized as in Example 8. In this example, the compositions (solutions) from Examples 5 and 7 were kept at ambient conditions, about 75° Fahrenheit, and the panels were immersed for a total of 40 minutes. Fig's. 6 and 7 (photos) show the improved corrosion resistance of these coating after 1000 hours of neutral salt fog per ASTM B 117. 1 EXAMPLE I l
Test specimens were anodized as in Example 8. In this example, the compositions (solutions) from Examples 5 and 6 were heated to 150° Fahrenheit, and the panels were immersed for a total of 5 minutes. Fig's. 7 and 8 (photos) show the corrosion resistance of these coatings after 1000 hours of neutral salt fog per ASTM B 117.
Table 2 compares the corrosion resistance results of the Examples based on numerical ratings from ASTM D 1654. hi the ASTM rating method, the best possible score is 10, meaning substantially no corrosion is evident on the test panel. Ratings decrease to 1, which represents substantially 100% corrosion of the panel surface. From the data in Table 2, it is evident that the process of this invention is an improvement over previous processes used for post treating or sealing phosphoric acid anodized aluminum and its alloys.
TABLE 2
Numerical corrosion ratings of the panels treated with the compositions (solutions) and the process of this invention, based on ASTM D 1654, had ratings as high as 10 (no corrosion) to a low of 1 (fully corroded) where there was no post-treatments. The ratings comprise an average of three rated panels for each condition.
For purposes of this invention, the water soluble surfactants or wetting agents can be added to the trivalent chromium solutions in amounts ranging from about 0 to 10 grams per liter and preferably 0.5 to about 1.5 grams per liter of the trivalent chromium solution. 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 coated substrate. The surfactants include at least one water soluble compound selected from the group consisting of the non-ionic, anionic, and cationic surfactants. Some known water soluble surfactants having the solubility at the required concentrations include the monocarboxyl imidoazoline, alkyl sulfate sodium salts (DUPONOL®), tridecyloxy poly(alkyleneoxy ethanol) ethoxylated or propoxylated alkyl phenol (IGEPAL®), alkyl sulfonamides, alkaryl sulfonates, palmitic alkanol amides (CENTROL®), octylphenyl polyethoxy ethanol (TRITON®), sorbitan monopahnitate (SPAN®), dodecylphenyl polyethylene glycol ether e.g. TERGITROL®, alkyl pyrrolidone, polyalkoxylated fatty acid esters, alkylbenzene sulfonates and mixtures thereof. Other known water soluble surfactants include the alkyl phenol alkyloxylates, ' preferably me nόnylphenol effiyloxylates, and the various anionic surfactants, having at least one sulfonate substituent in the phenyl ring, and the adducts of ethylene oxide with fatty amines. Other known water soluble compounds are found in "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 are added to retain the aqueous solution on the surface for sufficient contact tune. The thickeners employed are known inorganic and organic water soluble thickeners which can be added to the trivalent chromium solutions in effective amounts e.g. a sufficient concentration 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, methyl cellulose and mixtures thereof. Some of the less preferred thickeners include the water soluble inorganic thickeners such as colloidal silica, clays such as bentonite, starches, gum arabic, tragacanth, agar and various combinations.
After preparing the surface to be treated via conventional phosphoric acid anodizing techniques, the solution can be applied by immersion, spray or wipe-on techniques. The solution also can be used at elevated temperatures up to 65°C and optimally applied by immersion to further improve the corrosion resistance of phosphoric acid anodize coatings. Solution dwell time is about 1 to 60 minutes, depending on the solution temperature and concentration of the solution. After dwelling, the remaining solution is then thoroughly rinsed from the substrate with tap or deionized water. No additional chemical manipulations of the deposited film are necessary for excellent performance. However, an application of a strong oxidizing solution can yield a film with improved corrosion resistance. The additional corrosion resistance is presumed to be due to the hexavalent chromium formed in the film from the trivalent chromium. The aqueous sealer composition 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 the ability of this protective seal coating to provide the phosphoric acid anodized coatings with corrosion resistance better or at least equivalent to other known sealed anodic coatings produced with sulfuric, chromic, boric- sulfuric, or other known compositions. This capability has not been available before and offers new potential applications for phosphoric acid anodized in corrosive environments that were not previously possible. Phosphoric acid anodized aluminums have a major advantage over these other coatings in that its coating weights are typically 10 to 50 times lower. This yields significant weight savings and lower fatigue debit to structural aluminum alloys. In addition, this invention has the ability to enhance the performance of phosphoric acid anodize coatings currently being implemented as an adhesive bonding alternative to chromic acid anodizing. Phosphoric acid anodize coatings that have not been post treated are known to have inferior corrosion resistance, but are known also to have excellent bonding characteristics. This invention increases the corrosion performance of the anodized aluminums, while mamtaining the adhesive bonding strength of the coatings. The terms, for purposes of this invention, "solubility" and "water soluble" mean water solubility of the chemical compounds used in the solutions of this invention at least at the concentrations set-forth herein. While "ItSs invention nas"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

TOE INVENTION CLAIMED
1. Process for sealing phosphoric acid anodized aluminum and aluminum alloys to improve the corrosion resistance and maintain the adhesive bonding strength which comprises treating the anodized aluminum and its alloys with an acidic aqueous solution having a pH ranging from about 2.5 to 5.5; said acidic aqueous solution comprising, per liter of solution, from about 0.01 to 22 grams of a trivalent chromium compound, about 0.01 to 12 grams of an alkali metal hexatluorozirconate, about 0.0 to 12 grams of at least one fluorocompound selected from the group consisting of an alkali metal tetrafluoroborate, an alkali metal hexafluorosilicate and mixtures thereof, from about 0.001 to 10 grams of at least one divalent zinc compound, from 0.0 to about 10 grams of at least one water soluble thickener and from 0.0 to about 10 grams of at least one water- soluble surfactant.
2. The process of Claim 1 wherein the pH of the aqueous solution ranges from about 3.7 to 4.0 and the temperature of the aqueous solution ranges from about ambient to 200°F.
3. The process of Claim 2 wherein the trivalent chromium is a water soluble compound ranging from about 4.0 to 8.0 grams, the hexafluorozirconate is a water soluble compound ranging from about 6.0 to 10 grams, and the fluorocompounds are water soluble compounds ranging from about 0.12 to about 1.2 grams.
4. The process of Claim 3 wherein the thickener ranges from about 0.5 to 1.5 grams and the surfactant ranges from about 0.5 to 1.5 grams. 5. Process for sealing phosphoric acid anodized aluminum and aluminum alloys to improve the corrosion resistance and maintain the adhesive bonding strength which comprises treating the anodized aluminum and its alloys with an acidic aqueous solution having a pH ranging from about 3.7 to 4.0; said acidic aqueous solution comprising, per liter of solution, from about 4.0 to 8.0 grams of a trivalent chromium salt, about 6.0 to 10 grams of an alkali metal hexafluorozirconate, about 0.001 to 12 grams of at least one fluorocompound selected from the group consisting of an alkali metal tetrafluoroborate, an alkali metal hexaϋuorosilicate and mixtures thereof, from about 0.001 to 10 grams of at least one divalent zinc compound, from 0.0 to about 10 grams of at least one water soluble thickener and from 0.0 to about 10 grams of at least one water soluble surfactant.
6. The process of Claim 5 wherein the fluorocompound is present in the solution in an amount ranging from about 0.24 to 0.36 grams and the treated anodized aluminum is subsequently washed with water at temperatures ranging up to 2000F.
7. The process of Claim 5 wherein the thickener is a cellulose compound present in the acidic solution in amounts ranging from about 0.5 to 1.5 grains per liter.
8. The process of Claim 5 wherein the chromium salt is trivalent chromium sulfate.
9. The process of Claim 5 wherein the alkali metal zirconate is potassium hexafluorozirconate. 1 ϋ. TKe process of ClaiM'5 therein the trivalent chromium salt is chromium sulfate ranging from about 4.0 to 8.0 grams, the hexafluorozirconate is potassium hexafhiorozirconate ranging from about 6.0 to 10 grams, and the tetrafluoroborate or hexafluorosilicate ranges from about 0.24 to 0.36 grams.
11. The process of Claim 10 wherein the thickener is a cellulose compound ranging from about 0.5 to 1.5 grams.
12. The process of Claim 5 wherein the zinc compound is zinc acetate.
13. The process of Claim 11 wherein the chromium salt is trivalent chromium sulfate and the divalent zinc compound is zinc sulfate.
14. The process of Claim 11 wherein the water soluble surfactant is selected from the group consisting of water soluble non-ionic, anionic and cationic surfactants.
15. The process of Claim 14 wherein the zinc compound is a divalent zinc sulfate.
16. The process of Claim 15 wherein the zinc sulfate is present in the aqueous solution in an amount ranging from about 0.1 to 5.0 grams.
17. The process of Claim 5 wherein the chromium salt is chromium sulfate present in the aqueous solution in an amount ranging from 4.0 to 8.0 grams, the mixture of alkali metal tetrafluoroborate and hexafluorosilicate are present in the aqueous solution in an amount ranging from about 0.001 to 12 grams.
18. The process of Claim 17 wherein the zinc compound is zinc sulfate present in the aqueous solution in an amount ranging from about 0.1 to 5.0 grams.
19. The seal-coated phosphoric acid anodized aluminum and aluminum alloys of Claim 1.
20. The seal-coated phosphoric acid anodized aluminum and aluminum alloys of Claim 5.
EP05851693A 2005-02-15 2005-11-14 Process for sealing phosphoric acid anodized aluminums Not-in-force EP1853750B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11/058,533 US20060191599A1 (en) 2005-02-15 2005-02-15 Process for sealing phosphoric acid anodized aluminums
PCT/US2005/041425 WO2006088520A2 (en) 2005-02-15 2005-11-14 Process for sealing phosphoric acid anodized aluminums

Publications (3)

Publication Number Publication Date
EP1853750A2 true EP1853750A2 (en) 2007-11-14
EP1853750A4 EP1853750A4 (en) 2009-04-29
EP1853750B1 EP1853750B1 (en) 2011-04-20

Family

ID=36916892

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05851693A Not-in-force EP1853750B1 (en) 2005-02-15 2005-11-14 Process for sealing phosphoric acid anodized aluminums

Country Status (14)

Country Link
US (1) US20060191599A1 (en)
EP (1) EP1853750B1 (en)
JP (1) JP4805280B2 (en)
KR (1) KR101215772B1 (en)
CN (1) CN101146929B (en)
AT (1) ATE506469T1 (en)
AU (1) AU2005327547A1 (en)
BR (1) BRPI0519983A2 (en)
CA (1) CA2598390A1 (en)
DE (1) DE602005027616D1 (en)
DK (1) DK1853750T3 (en)
ES (1) ES2365403T3 (en)
MX (1) MX2007009800A (en)
WO (1) WO2006088520A2 (en)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7452454B2 (en) * 2001-10-02 2008-11-18 Henkel Kgaa Anodized coating over aluminum and aluminum alloy coated substrates
CN101384751B (en) * 2006-02-14 2013-01-02 汉高股份及两合公司 Composition and processes of a dry-in-place trivalent chromium corrosion-resistant coating for use on metal surfaces
CA2651393C (en) * 2006-05-10 2016-11-01 Henkel Ag & Co. Kgaa Improved trivalent chromium-containing composition for use in corrosion resistant coatings on metal surfaces
JP5288216B2 (en) * 2009-02-27 2013-09-11 日立オートモティブシステムズ株式会社 Disc brake
US8273190B2 (en) 2009-05-29 2012-09-25 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
US9187839B2 (en) 2010-10-07 2015-11-17 Michael Sheehy Process for the manufacture of sealed anodized aluminum components
WO2012061872A1 (en) * 2010-11-08 2012-05-18 Mezurx Pty Ltd Sample analyser
CN102817059B (en) * 2012-08-18 2015-05-20 佛山金兰铝厂有限公司 Novel hole sealing tank liquid for aluminum alloy oxidation section and sealing method by using the same
ITMI20122229A1 (en) * 2012-12-21 2014-06-22 Campagnolo Srl BICYCLE COMPONENT INCLUDING AN ALUMINUM BODY AND A COMPOSITE BODY, AND METHOD OF MANUFACTURING SUCH A COMPONENT
US10156016B2 (en) 2013-03-15 2018-12-18 Henkel Ag & Co. Kgaa Trivalent chromium-containing composition for aluminum and aluminum alloys
JPWO2017199865A1 (en) * 2016-05-17 2019-03-14 Nok株式会社 Method for preventing corrosion of aluminum-based member surfaces
RU2758664C1 (en) * 2018-01-30 2021-11-01 Прк-Десото Интернэшнл, Инк. Systems and methods for processing metal substrate
KR102500400B1 (en) * 2018-03-29 2023-02-15 니혼 파커라이징 가부시키가이샤 Surface treatment agent, aluminum or aluminum alloy material having surface treatment film, and manufacturing method thereof
JP7118402B2 (en) * 2018-04-26 2022-08-16 奥野製薬工業株式会社 Sealing treatment liquid for anodized film of aluminum alloy, concentrated liquid and sealing treatment method
US11155928B2 (en) * 2019-12-19 2021-10-26 The United States Of America As Represented By The Secretary Of The Navy Electrolytic process for deposition of chemical conversion coatings
FR3106838B1 (en) * 2020-01-31 2022-01-14 Safran Aircraft Engines ALUMINUM ALLOY CLOGGING PROCESS
FR3106837B1 (en) * 2020-01-31 2023-05-12 Safran Aerosystems SURFACE TREATMENT PROCESS FOR ALUMINUM-BASED PARTS
FR3140382A1 (en) 2022-10-04 2024-04-05 Safran Landing Systems PROCESS FOR POST-ANODIZATION SEALING OF ALUMINUM AND ALUMINUM ALLOYS WITHOUT USING CHROME

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4084014A (en) * 1976-10-05 1978-04-11 Juan Brugarolas Fabregas Process for sealing anodic oxidation layers on aluminium surfaces and its alloys
US4467028A (en) * 1982-07-12 1984-08-21 Polychrome Corporation Acid interlayered planographic printing plate
US5304257A (en) * 1993-09-27 1994-04-19 The United States Of America As Represented By The Secretary Of The Navy Trivalent chromium conversion coatings for aluminum
US6511532B2 (en) * 2000-10-31 2003-01-28 The United States Of America As Represented By The Secretary Of The Navy Post-treatment for anodized aluminum
US6663700B1 (en) * 2000-10-31 2003-12-16 The United States Of America As Represented By The Secretary Of The Navy Post-treatment for metal coated substrates
EP1378585A1 (en) * 2002-06-27 2004-01-07 United Technologies Corporation Corrosion resistant trivalent chromium phosphated chemical conversion coatings

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4786336A (en) * 1985-03-08 1988-11-22 Amchem Products, Inc. Low temperature seal for anodized aluminum surfaces
JPH03122300A (en) * 1989-10-06 1991-05-24 Johoku Riken Kogyo:Kk Surface treatment of aluminum alloy
JP2579234B2 (en) * 1990-04-25 1997-02-05 スカイアルミニウム株式会社 Aluminum fin material for heat exchanger and method for producing the same
US5374347A (en) * 1993-09-27 1994-12-20 The United States Of America As Represented By The Secretary Of The Navy Trivalent chromium solutions for sealing anodized aluminum
GB9422952D0 (en) * 1994-11-14 1995-01-04 Secr Defence Corrosion inhibitor
JP2001152392A (en) * 1999-11-24 2001-06-05 Toyama Prefecture Alkali resistant aluminum oxide composite film and producing method therefor
US6669764B1 (en) * 2000-10-31 2003-12-30 The United States Of America As Represented By The Secretary Of The Navy Pretreatment for aluminum and aluminum alloys

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4084014A (en) * 1976-10-05 1978-04-11 Juan Brugarolas Fabregas Process for sealing anodic oxidation layers on aluminium surfaces and its alloys
US4467028A (en) * 1982-07-12 1984-08-21 Polychrome Corporation Acid interlayered planographic printing plate
US5304257A (en) * 1993-09-27 1994-04-19 The United States Of America As Represented By The Secretary Of The Navy Trivalent chromium conversion coatings for aluminum
US6511532B2 (en) * 2000-10-31 2003-01-28 The United States Of America As Represented By The Secretary Of The Navy Post-treatment for anodized aluminum
US6663700B1 (en) * 2000-10-31 2003-12-16 The United States Of America As Represented By The Secretary Of The Navy Post-treatment for metal coated substrates
EP1378585A1 (en) * 2002-06-27 2004-01-07 United Technologies Corporation Corrosion resistant trivalent chromium phosphated chemical conversion coatings

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2006088520A2 *

Also Published As

Publication number Publication date
CA2598390A1 (en) 2006-08-24
JP4805280B2 (en) 2011-11-02
EP1853750A4 (en) 2009-04-29
KR101215772B1 (en) 2013-01-10
WO2006088520A3 (en) 2007-01-18
MX2007009800A (en) 2007-09-27
WO2006088520A2 (en) 2006-08-24
ES2365403T3 (en) 2011-10-04
DK1853750T3 (en) 2011-06-20
CN101146929A (en) 2008-03-19
AU2005327547A1 (en) 2006-08-24
US20060191599A1 (en) 2006-08-31
JP2008530362A (en) 2008-08-07
CN101146929B (en) 2010-08-11
DE602005027616D1 (en) 2011-06-01
KR20070121674A (en) 2007-12-27
EP1853750B1 (en) 2011-04-20
ATE506469T1 (en) 2011-05-15
BRPI0519983A2 (en) 2009-08-18

Similar Documents

Publication Publication Date Title
EP1853750B1 (en) Process for sealing phosphoric acid anodized aluminums
CA2466045C (en) Post-treatment for anodized aluminum
EP1451388B1 (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
CA2513875C (en) Pretreatment for aluminum and aluminum alloys
US20060180247A1 (en) Process for preparing chromium conversion coatings for iron and iron alloys
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
WO2006088518A2 (en) Process for preparing chromium conversion coatings for iron and iron alloys

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20070815

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20090326

RIC1 Information provided on ipc code assigned before grant

Ipc: C23C 22/34 20060101ALI20090320BHEP

Ipc: C25D 11/24 20060101AFI20090320BHEP

Ipc: C23C 22/83 20060101ALI20090320BHEP

17Q First examination report despatched

Effective date: 20100323

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: THE UNITED STATES OF AMERICA, AS REPRESENTED BY TH

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 602005027616

Country of ref document: DE

Date of ref document: 20110601

Kind code of ref document: P

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602005027616

Country of ref document: DE

Effective date: 20110601

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: GR

Ref legal event code: EP

Ref document number: 20110401695

Country of ref document: GR

Effective date: 20110829

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20110420

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2365403

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20111004

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110822

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110420

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110420

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110820

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110420

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110420

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110420

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110420

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110420

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110420

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110420

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110420

26N No opposition filed

Effective date: 20120123

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602005027616

Country of ref document: DE

Effective date: 20120123

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111130

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111130

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111130

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111114

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111114

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110720

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110420

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20131105

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 20141124

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20141126

Year of fee payment: 10

Ref country code: GB

Payment date: 20141120

Year of fee payment: 10

Ref country code: SE

Payment date: 20141120

Year of fee payment: 10

Ref country code: ES

Payment date: 20141120

Year of fee payment: 10

Ref country code: GR

Payment date: 20141120

Year of fee payment: 10

Ref country code: FI

Payment date: 20141119

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20141120

Year of fee payment: 10

Ref country code: FR

Payment date: 20141118

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20141121

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20141125

Year of fee payment: 10

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 602005027616

Country of ref document: DE

Representative=s name: RIPPER, SIGRID, DIPL.-PHYS. DR.RER.NAT., DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602005027616

Country of ref document: DE

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

Effective date: 20151130

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20151114

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20151114

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160602

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20151201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20160729

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20151115

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20151201

REG Reference to a national code

Ref country code: GR

Ref legal event code: ML

Ref document number: 20110401695

Country of ref document: GR

Effective date: 20160602

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160601

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20151114

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20151130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20151130

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20161230

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20151115

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20151114

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20151130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20151114