EP0488430A2 - Revêtement de conversion au cobalt, sans chromate - Google Patents

Revêtement de conversion au cobalt, sans chromate Download PDF

Info

Publication number
EP0488430A2
EP0488430A2 EP91202181A EP91202181A EP0488430A2 EP 0488430 A2 EP0488430 A2 EP 0488430A2 EP 91202181 A EP91202181 A EP 91202181A EP 91202181 A EP91202181 A EP 91202181A EP 0488430 A2 EP0488430 A2 EP 0488430A2
Authority
EP
European Patent Office
Prior art keywords
cobalt
solution
salt
conversion coating
substrate
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
EP91202181A
Other languages
German (de)
English (en)
Other versions
EP0488430A3 (en
EP0488430B1 (fr
Inventor
Matthias P. Schriever
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.)
Boeing Co
Original Assignee
Boeing Co
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 Boeing Co filed Critical Boeing Co
Publication of EP0488430A2 publication Critical patent/EP0488430A2/fr
Publication of EP0488430A3 publication Critical patent/EP0488430A3/en
Application granted granted Critical
Publication of EP0488430B1 publication Critical patent/EP0488430B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C23C22/68—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 solutions with pH between 6 and 8
    • 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 environmental-quality invention is in the field of chemical conversion coatings formed on metal substrates, for example, on aluminum substrates. More particularly, one aspect of the invention is a new type of oxide coating (which I refer to as a "cobalt conversion coating") which is chemically formed on metal substrates.
  • the invention enhances the quality of the environment of mankind by contributing to the maintenance of air and water quality.
  • chemical conversion coatings are formed chemically by causing the surface of the metal to be "converted" into a tightly adherent coating, all or part of which consists of an oxidized form of the substrate metal.
  • Chemical conversion coatings can provide high corrosion resistance as well as strong bonding affinity for paint.
  • the industrial application of paint (organic finishes) to metals generally requires the use of a chemical conversion coating, particularly when the performance demands are high.
  • aluminum protects itself against corrosion by forming a natural oxide coating, the protection is not complete.
  • aluminum alloys particularly the high-copper 2000-series aluminum alloys, such as alloy 2024-T3, corrode much more rapidly than pure aluminum.
  • the first is by anodic oxidation (anodization) in which the aluminum component is immersed in a chemical bath, such as a chromic or sulfuric acid bath, and an electric current is passed through the aluminum component and the chemical bath.
  • a chemical bath such as a chromic or sulfuric acid bath
  • an electric current is passed through the aluminum component and the chemical bath.
  • the resulting conversion coating on the surface of the aluminum component offers resistance to corrosion and a bonding surface for organic finishes.
  • the second type of process is by chemically producing a conversion coating, which is commonly referred to as a chemical conversion coating, by subjecting the aluminum component to a chemical solution, such as a chromic acid solution, but without using an electric current in the process.
  • a chemical solution such as a chromic acid solution
  • the chemical solution may be applied by immersion application, by manual application, or by spray application.
  • the resulting conversion coating on the surface of the aluminum component offers resistance to corrosion and a bonding surface for organic finishes.
  • the present invention relates to this second type of process for producing chemical conversion coatings.
  • the chemical solution may be applied by immersion application, by various types of manual application, or by spray application.
  • chromic acid process for forming chemical conversion coatings on aluminum substrates is described in various embodiments in Ostrander et al. U.S. Patent 2,796,370 and Ostrander et al. U.S. Patent 2,796,371, in military process specification MIL-C-5541, and in Boeing Process Specification BAC 5719.
  • These chromic acid chemical conversion baths contain hexavalent chromium, fluorides, and cyanides, all of which present significant environmental as well as health and safety problems.
  • chromic acid conversion bath such as ALODINE 1200
  • Cr03 - "chromic acid” hexavalent chromium
  • NaF - sodium fluoride KBF4 - potassium tetrafluoroborate
  • K2ZrF6 - potassium hexafluorozirconate K3Fe(CN)6 - potassium ferricyanide
  • HNO3 - nitric acid for pH control
  • Chromic acid conversion films as formed on aluminum substrates, meet a 168 hours corrosion resistance criterion, but they primarily serve as a surface substrate for paint adhesion. Because of their relative thinness and low coating weights (40-150 milligrams/ft2), chromic acid conversion coatings do not cause a fatigue life reduction in the aluminum structure.
  • FIGS. 1-20 are photomicrographs (scanning electron microscope operated at 20 KV) of aluminum alloy 2024-T3 test panels with cobalt conversion coatings made by the invention.
  • FIGS. 1-16 show surface views and fracture views of unsealed cobalt conversion coatings.
  • the photomicrographs of FIGS. 1-16 reveal a highly porous surface oxide (unsealed cobalt conversion coatings) with a thickness range of about 0.12 to 0.14 micron (1200 to 1400 Angstroms).
  • FIGS. 1-4 show an unsealed cobalt conversion coating formed by a 20 minute immersion in a typical cobalt coating solution.
  • FIGS. 5-8 show an unsealed cobalt conversion coating formed by a 30 minute immersion in a typical cobalt coating solution.
  • FIGS. 9-12 show an unsealed cobalt conversion coating formed by a 50 minute immersion in a typical cobalt coating solution.
  • FIGS. 13-16 show an unsealed cobalt conversion coating formed by a 60 minute immersion in a typical cobalt coating solution. There were only minor differences in oxide coating thickness between these immersion times. This suggests that at any given bath operating temperature, the oxide structure becomes self limiting.
  • FIGS. 17-20 show surface views and fracture views of a sealed cobalt conversion coating.
  • FIG. 1 is a photomicrograph at X10,000 magnification of a test panel showing a cobalt conversion coating 130 of the invention.
  • the photomicrograph is a top view, from an elevated angle, of the upper surface of oxide coating 130.
  • the top of oxide coating 130 is porous and looks like a layer of chow mein noodles.
  • the porosity of oxide coating 130 gives excellent paint adhesion results.
  • This test panel was immersed in a cobalt conversion coating solution for 20 minutes.
  • the white bar is a length of 1 micron.
  • FIG. 2 is a photomicrograph at X50,000 magnification of the test panel of FIG. 1.
  • the photomicrograph is a top view, from an elevated angle, of the upper surface of oxide coating 130.
  • FIG. 2 is a close-up, at higher magnification, of a small area of FIG. 1.
  • the white bar is a length of 1 micron.
  • FIG. 3 is a photomicrograph at X10,000 magnification of a test panel showing a side view of a fractured cross section of a cobalt conversion coating 130 of the invention.
  • the fractured cross section of the aluminum substrate of the test panel is indicated by reference numeral 132.
  • This test panel was immersed in a coating bath for 20 minutes. To make the photomicrograph, the test panel was bent and broken off to expose a cross section of oxide coating 130.
  • the white bar is a length of 1 micron.
  • FIG. 4 is a photomicrograph at X50,000 magnification of the test panel of FIG. 3 showing a side view of a fractured cross section of cobalt conversion coating 130 of the invention.
  • FIG. 4 is a close-up, at higher magnification, of a small area of FIG. 3.
  • the aluminum substrate of the test panel is indicated by reference numeral 132.
  • the white bar is a length of 1 micron.
  • Oxide coating 130 has a vertical thickness of about 0.12-0.14 micron.
  • FIG. 5 is a photomicrograph at X10,000 magnification of another test panel showing another cobalt conversion coating 150 of the invention.
  • the photomicrograph is a top view, from an elevated angle, of the upper surface of oxide coating 150.
  • the top of oxide coating 150 is porous and looks like a layer of chow mein noodles.
  • This test panel was immersed in a cobalt conversion coating solution for 30 minutes.
  • the white bar is a length of 1 micron.
  • FIG. 6 is a photomicrograph at X50,000 magnification of the test panel of FIG. 5.
  • the photomicrograph is a top view, from an elevated angle, of the upper surface of oxide coating 150.
  • FIG. 6 is a close-up, at higher magnification, of a small area of FIG. 5.
  • the white bar is a length of 1 micron.
  • FIG. 7 is a photomicrograph at X10,000 magnification of a test panel showing a side view of a fractured cross section of cobalt conversion coating 150 of the invention.
  • the aluminum substrate of the test panel is indicated by reference numeral 152.
  • This test panel was immersed in a coating bath for 30 minutes. To make the photomicrograph, the test panel was bent and broken off to expose a cross section of oxide coating 150.
  • the white bar is a length of 1 micron.
  • FIG. 8 is a photomicrograph at X50,000 magnification of the test panel of FIG. 7 showing a side view of a fractured cross section of cobalt conversion coating 150 of the invention.
  • FIG. 8 is a close-up, at higher magnification, of a small area of FIG. 7.
  • the aluminum substrate of the test panel is indicated by reference numeral 152.
  • the white bar is a length of 1 micron.
  • Oxide coating 150 has a vertical thickness of about 0.12-0.14 micron.
  • FIG. 9 is a photomicrograph at X10,000 magnification of a test panel showing a cobalt conversion coating 190 of the invention.
  • the photomicrograph is a top view, from an elevated angle, of the upper surface of oxide coating 190.
  • the top of oxide coating 190 is porous and looks like a layer of chow mein noodles.
  • This test panel was immersed in a cobalt conversion coating solution for 50 minutes.
  • the oblong object indicated by reference numeral 192 is an impurity, believed to be a piece of oxidized material, on top of oxide coating 190.
  • the white bar is a length of 1 micron.
  • FIG. 10 is a photomicrograph at X50,000 magnification of the test panel of FIG. 9.
  • the photomicrograph is a top view, from an elevated angle, of the upper surface of oxide coating 190.
  • FIG. 10 is a close-up, at higher magnification, of a small area of FIG. 9.
  • the roundish object indicated by reference numeral 192a is an unidentified impurity on top of oxide coating 190.
  • the white bar is a length of 1 micron.
  • FIG. 11 is a photomicrograph at X10,000 magnification of a test panel showing a side view of a fractured cross section of a cobalt conversion coating 190 of the invention.
  • the fractured cross section of the aluminum substrate of the test panel is indicated by reference numeral 194.
  • This test panel was immersed in a coating bath for 50 minutes. To make the photomicrograph, the test panel was bent and broken off to expose a cross section of oxide coating 190.
  • the white bar is a length of 1 micron.
  • FIG. 12 is a photomicrograph at X50,000 magnification of the test panel of FIG. 11 showing a side view of a fractured cross section of cobalt conversion coating 190 of the invention.
  • FIG. 12 is a close-up, at higher magnification, of a small area of FIG. 11.
  • the aluminum substrate of the test panel is indicated by reference numeral 194.
  • the white bar is a length of 1 micron.
  • Oxide coating 190 has a vertical thickness of about 0.12-0.14 micron.
  • FIG. 13 is a photomicrograph at X10,000 magnification of another test panel showing a cobalt conversion coating 230 of the invention.
  • the photomicrograph is a top view, from an elevated angle, of the upper surface of oxide coating 230.
  • the top of oxide coating 230 is porous and looks like a layer of chow mein noodles.
  • This test panel was immersed in a cobalt conversion coating solution for 60 minutes.
  • the white bar is a length of 1 micron.
  • FIG. 14 is a photomicrograph at X50,000 magnification of the test panel of FIG. 13.
  • the photomicrograph is a top view, from an elevated angle, of the upper surface of oxide coating 230.
  • FIG. 14 is a close-up, at higher magnification, of a small area of FIG. 13.
  • the white bar is a length of 1 micron.
  • FIG. 15 is a photomicrograph at X10,000 magnification of a test panel showing a side view of a fractured cross section of cobalt conversion coating 230 of the invention.
  • the aluminum substrate of the test panel is indicated by reference numeral 232.
  • This test panel was immersed in the coating bath for 60 minutes. To make the photomicrograph, the test panel was bent and broken off to expose a cross section of oxide coating 230.
  • the white bar is a length of 1 micron.
  • FIG. 16 is a photomicrograph at X50,000 magnification of the test panel of FIG. 15 showing a side view of a fractured cross section of cobalt conversion coating 230 of the invention.
  • FIG. 16 is a close-up, at higher magnification, of a small area of FIG. 15.
  • the white bar is a length of 1 micron.
  • Oxide coating 150 has a vertical thickness of about 0.12-0.14 micron.
  • FIG. 17 is a photomicrograph at X10,000 magnification of another test panel showing a sealed cobalt conversion coating 270 of the invention.
  • the photomicrograph is a top view, from an elevated angle, of the upper surface of sealed oxide coating 270.
  • This test panel was immersed in a sealing solution for 20 minutes.
  • Sealed oxide coating 270 is not as porous as an unsealed oxide coating, the pores of the oxide coating being partially filled by hydration as a result of immersion in a sealing solution.
  • the partial sealing of the oxide coating gives reduced paint adhesion results, but excellent corrosion resistance performance.
  • the whitish areas identified by reference numeral 274 are believed to be impurities from the sealing solution.
  • the white bar is a length of 1 micron.
  • FIG. 18 is a photomicrograph at X50,000 magnification of the test panel of FIG. 17.
  • the photomicrograph is a top view, from an elevated angle, of the upper surface of sealed oxide coating 270.
  • FIG. 18 is a close-up, at higher magnification, of a small area of FIG. 17.
  • Sealed oxide coating 270 is not as porous as an unsealed oxide coating, the pores of the oxide coating being partially filled by hydration as a result of immersion in a sealing solution.
  • the white bar is a length of 1 micron.
  • FIG. 19 is a photomicrograph at X10,000 magnification of a test panel showing a side view of a fractured cross section of sealed cobalt conversion coating 270 of the invention.
  • the aluminum substrate of the test panel is indicated by reference numeral 272. This test panel was immersed in the sealing bath for 20 minutes. To make the photomicrograph, the test panel was bent and broken off to expose a cross section of oxide coating 270.
  • the white bar is a length of 1 micron.
  • FIG. 20 is a photomicrograph at X50,000 magnification of the test panel of FIG. 19 showing a side view of a fractured cross section of sealed cobalt conversion coating 270 of the invention.
  • FIG. 20 is a close-up, at higher magnification, of a small area of FIG. 19.
  • the white bar is a length of 1 micron.
  • Sealed oxide coating 270 has a vertical thickness of about 0.12-0.14 micron.
  • the first class is a cobalt conversion coating consisting of an oxide structure in unsealed condition and suitable for use in service where paint adhesion is especially important.
  • the second class is a cobalt conversion coating consisting of an oxide structure in sealed condition and suitable for use in service where bare metal corrosion resistance performance is desired.
  • cobalt coordination complexes are formed where the portion of the complex which includes the ligand (the bracketed portion in equations (1)-(5)) is negatively charged, i.e., (8) [Co(NO2)6]3 ⁇ and the complete complex is (9) Me3[Co(NO2)6] where Me corresponds to Na, K, or Li (alkali metal ions).
  • This cobalt nitrite complex bath chemistry (equation (1)) has a distinct advantage over the previously described cobalt hexammine complex chemistry (equation (6)) in that pH control of the cobalt hexanitrite complex bath is not required.
  • cobalt-III hexanitrite complexes are capable of forming oxide structures on aluminum substrates.
  • the oxidizing ability of the cobalt-III hexanitrite complex is believed to be responsible for the formation of the observed oxide films (which I refer to as "cobalt conversion coatings") on aluminum substrates.
  • the formation of oxide structures has been confirmed by instrumental analysis (Auger analysis and electron microscopy) of the coating.
  • the photomicrographs in FIGS. 1-20 illustrate the appearance of the cobalt conversion coating of the invention.
  • cobalt salts and metal nitrite salts are operable for cobalt complexing.
  • cobalt-II salts which are operable in water solution are: cobalt nitrate, Co(NO3)2 ⁇ 6H2O; cobalt chloride, CoCl2 ⁇ 6H2O; cobaltous sulfate, CoSO4; cobaltous acetate, Co(CH3COO)2 ⁇ 4H2O; and cobaltous basic carbonate, 2CoCO3 ⁇ Co(OH)2 ⁇ H2O.
  • a nitrite salt such as NaNO2, KNO2, or LiNO2.
  • cobalt-II salts may be used if they possess a minimum solubility in water or in a water solution containing a metal nitrite salt.
  • the minimum solubility needed is 25 grams per 100 ml of water at 20°C (68°F) or 25 grams per 100 ml of water solution containing a metal nitrite salt at 20°C (68°F).
  • the preferred reactants are Co(NO3)2 ⁇ 6H2O and NaNO2, since cobalt nitrite complexes formed with potassium or lithium nitrite are of limited solubility and will eventually drop out of an aqueous solution.
  • a preferred chemical additive is an oxidizer, preferably hydrogen peroxide, H2O2.
  • the function of the oxidizer is to oxidize the cobalt-II ions in solution to cobalt-III ions. Care must be taken that an excess amount of chemical oxidizer is not used because an excess would have the undesired effect of oxidizing the nitrite ions in solution to nitrate ions.
  • the stream of air flowing into the tank functions as an oxidizer, so the presence of hydrogen peroxide is not essential for operability.
  • the hydrogen peroxide increases the rate of oxidation of the cobalt-II ions in solution to cobalt-III ions and therefore is useful for commercial practice of the invention in that the solution becomes operational in a shorter period of time.
  • reaction accelerator chemical such as sodium bromide (NaBr) or sodium iodide (NaI) may be added to the solution.
  • NaBr sodium bromide
  • NaI sodium iodide
  • the reaction accelerator was found to have the effect of accelerating the formation of the oxide conversion coatings on aluminum alloy substrates as compared to solutions of cobalt-III hexanitrite complexes which did not contain this additive. The presence of the accelerator is not essential for operability. The accelerator increases the rate of formation of the oxide conversion coatings on aluminum alloys and therefore is useful for commercial practice of the invention.
  • the preferred chemical reactants and additives are: Cobalt nitrate Co(N03)2 ⁇ 6H2O Sodium nitrite NaNO2 Hydrogen peroxide (oxidizer) H2O2 Sodium iodide (accelerator) NaI
  • the concentration of dissolved cobalt-II salt used may be from about 0.1 moles per gallon of final solution up to the saturation limit of the cobalt-II salt employed.
  • the concentration of dissolved metal nitrite salt may be from about 0.6 to 12 moles per gallon of final solution.
  • the concentration of oxidizer, such as hydrogen peroxide may be from complete omission up to about 0.5 moles per gallon of final solution. As stated above, an excess amount of hydrogen peroxide has undesired effects.
  • the concentration of accelerator salt, such as NaI may be from complete omission up to the solubility limit of the accelerator in the solution.
  • the pH of the bath may be from about 7.0 to 7.2.
  • the temperature of the bath may be from about 68°F to 150°F; below 100°F coating formation is very slow; above 150°F gradual decomposition of the cobalt-III hexanitrite complex occurs.
  • the immersion time may be from about 3 minutes to 60 minutes.
  • the cobalt conversion coating should be applied after all trimming and fabrication have been completed. Parts, where solution entrapment is possible, should not be subjected to immersion alkaline cleaning or immersion deoxidizing; manual cleaning and manual deoxidizing procedures should be used to obtain water break-free surfaces before applying cobalt conversion treatment.
  • a water break-free surface is a surface which maintains a continuous water film for a period of at least 30 seconds after having been sprayed or immersion rinsed in clean water at a temperature below 100°F.
  • Vapor degrease may be performed in accordance with Boeing Process Specification BAC 5408, emulsion clean in accordance with Boeing Process Specification BAC 5763, or solvent clean in accordance with Boeing Process Specification BAC 5750 if parts are greasy or oily. Parts with open faying surfaces or spot-welded joints where solution entrapment is possible should be immersed in cold water (or in hot and cold water) for 2 minutes after precleaning.
  • Alkaline clean and rinse may be performed in accordance with Boeing Process Specification BAC 5744 or Boeing Process Specification BAC 5749 except for parts with open faying surfaces or spot welded joints, in which case, rinsing should be for at least 10 minutes using agitation with multiple immersions (a minimum of four times) followed by manual spray rinsing as required to prevent solution entrapment.
  • Deoxidize and rinse may be performed in accordance with Boeing Process Specification BAC 5765 except for parts where solution entrapment is possible, which parts may be rinsed using the method described above under "Alkaline Cleaning". Castings may be deoxidized by either of the following methods:
  • Example 1 Component Make-Up Per Gallon Of Final Solution Control Limits Cobalt(ous) nitrate, Co(NO3)2 ⁇ 6H20 (hexahydrate) 85 gm (about 0.29 mole) 75-95 gm/gal Sodium nitrite, NaNO2 242 gm (about 3.51 moles) 227-246 gm/gal Sodium Iodide, NaI 90 gm (about 0.60 moles) 83-99 gm/gal Hydrogen peroxide, H2O2 (30 vol. %) 30-50 ml (about 0.3-0.5 moles of H202) Water balance Temperature 120 ⁇ 5° F pH 7.0 - 7.2
  • Example 2 The formulation of Example 1, with a molar ratio of nitrite salt to cobalt salt of about 12 to 1, is useful for producing oxide coatings exhibiting high paint adhesion in unsealed condition.
  • Example 2 Component Make-Up Per Gallon Of Final Solution Control Limits Cobalt(ous) chloride, CoCl2 ⁇ 6H20 (hexahydrate) 69 gm (about 0.29 mole) Sodium nitrite, NaN02 242 gm (about 3.51 moles) Sodium iodide, NaI 90 gm (about 0.60 moles) Hydrogen peroxide, H2O2 (30 vol. %) 30-50 ml (about 0.3-0.5 moles of H2O2) Water balance Temperature 120-150°F pH 7.0 - 7.2
  • Example 2 The formulation of Example 2, also having a molar ratio of nitrite salt to cobalt salt of about 12 to 1, is useful for producing oxide coatings possessing high paint adhesion properties in unsealed condition.
  • Example 3 Component Make-Up Per Gallon Of Final Solution Control Limits Cobalt acetate, Co(CH3COO)2 ⁇ 4H20 73 gm (about 0.29 moles) Sodium nitrite, NaNO2 242 gm (about 3.51 moles) Sodium iodide, NaI (accelerator) 90 gm (about 0.60 moles) Hydrogen peroxide, H2O2 (30 vol. %) 30-50 ml (about 0.3-0.5 moles of H2O2) Water balance Temperature 120-150°F pH 7.0 - 7.2
  • any 2-valent soluble cobalt salt may be reacted with any soluble nitrite salt to form 3-valent cobalt hexanitrite complexes.
  • this type of complexing is not restricted to nitrites only.
  • cyanide salts were used (i.e., sodium cyanide, NaCN) to form hexacyano complexes of the type shown below (10) Me3[Co(CN)6 ] and have yielded satisfactory conversion coatings on aluminum alloys.
  • cyanide complexes will not be used because of environmental considerations.
  • Nickel sulfate NiS04 ⁇ 6H20 (hexahydrate) 152 gm (about 0.58 moles) 144-159 gm Ammonium nitrate, NH4NO3 114 gm (about 1.42 moles) 105-121 gm Manganese acetate, Mn(CH3COO)2 ⁇ 4H2O 76 gm (about 0.31 moles) 68-84 gm Operating temperature 185 ⁇ 5° F
  • the immersion time in the sealing solution may be about 10-30 minutes, with 15 minutes being preferred.
  • the sealing solution is believed to seal the cobalt conversion coating by a hydration mechanism.
  • FIGS. 17-20, particularly FIG. 18, show a sealed cobalt conversion coating 270.
  • Other sealing solutions which may be employed are as follows:
  • Solutions 1-3 are not preferred because they lose their effectiveness over a period of time, whereas the solution in Example 4 has a long life.
  • a continuous operating temperature range of the cobalt conversion tank of 120-140°F yields optimum results with respect to coating performance on aluminum alloy substrates.
  • Optimum paint adhesion is obtained when the tank is operated at or near 120°F, while optimum corrosion resistance performance is given at 140°F in combination with the subsequent seal process.
  • Immersion times in the cobalt conversion tank have an effect on the oxide coating thickness as measured by the coating weight (in unsealed condition) ranging from 40 to 60 mg/ft2.
  • An optimum immersion time for maximum paint adhesion is 15 minutes and for maximum corrosion resistance performance is 30 minutes.
  • Salt spray corrosion resistance of cobalt conversion coatings produced by the above processes varies over a wide range, depending on reactant selection, immersion times, and bath operating temperatures. Preferred results are obtained when the formulation of Example 1 is utilized at immersion times of 30 minutes. In this way, sealed oxide coatings have been produced with 168 hrs. of salt spray corrosion resistance when sealed with the seal solution as described herein and tested in accordance with ASTM B117.
  • Paint adhesion tests were conducted using aircraft paints qualified to Boeing Material Specification BMS 10-11 (a highly crosslinked epoxy primer) and BMS 10-60 (a highly crosslinked urethane topcoat).
  • BMS 10-11 a highly crosslinked epoxy primer
  • BMS 10-60 a highly crosslinked urethane topcoat
  • corrosion resistance and paint adhesion performance properties have an inverse relationship. In general, where corrosion resistance is at a maximum, paint adhesion is at a minimum, and vice versa.
  • the optional post-conversion step consisting of immersion into a heated solution (at 185 ⁇ 5°F) of NiS04/NH4NO3/Mn-acetate minimizes this problem by maintaining sufficient paint adhesion values while maintaining high corrosion resistance properties.
  • ESCA electron spectroscopy for chemical analysis (also known as XPS or X-ray photoelectron spectroscopy).)
  • the cobalt conversion coating consists of a mixture of oxides, namely, aluminum oxide, Al2O3, as the largest volume percent, and cobalt oxides, CoO, Co3O4, and Co2O3.
  • the term "largest volume percent” means that the volume of this oxide exceeds the volume of any other oxide which is present, but the term “largest volume percent” does not necessarily imply that the volume of this oxide is more than 50 volume percent.
  • the data further shows that in the lower portion of the oxide coating (that is, next to the aluminum substrate), the largest volume percent is Al2O3.
  • the middle portion of the oxide coating is a mixture of CoO, Co3O4, Co2O3, and Al2O3.
  • the data shows that in the top portion of the oxide coating, the largest volume percent is a mixture of Co3O4 and Co2O3.
  • FIGS. 1-4 show a cobalt conversion coating 130 (in the unsealed condition) formed by a 20 minute immersion in a typical cobalt conversion coating solution.
  • FIGS. 5-8 show a cobalt conversion coating 150 (in the unsealed condition) formed by a 30 minute immersion in a typical cobalt conversion coating solution.
  • FIGS. 9-12 show a cobalt conversion coating 190 (in the unsealed condition) formed by a 50 minute immersion in a typical cobalt conversion coating solution.
  • FIGS. 1-4 show a cobalt conversion coating 130 (in the unsealed condition) formed by a 20 minute immersion in a typical cobalt conversion coating solution.
  • FIGS. 5-8 show a cobalt conversion coating 150 (in the unsealed condition) formed by a 30 minute immersion in a typical cobalt conversion coating solution.
  • FIGS. 9-12 show a cobalt conversion coating 190 (in the unsealed condition) formed by a 50 minute immersion in a typical cobalt
  • FIGS. 13-16 show a cobalt conversion coating 230 (in the unsealed condition) formed by a 60 minute immersion in a typical cobalt conversion coating solution. Comparing FIGS. 1-4, FIGS. 5-8, FIGS. 9-12, and FIGS. 13-16, there does not appear to be any significant structural difference between coating 130, coating 150, coating 190, and coating 230. This suggests that at any given bath operating temperature, the oxide coating becomes self limiting.
  • the top surface of the cobalt conversion coating as shown in FIGS. 1, 2, 5, 6, 9, 10, 13, and 14 is porous and bears a resemblance to chow mein noodles. This oxide structure provides appreciable surface area and porosity for good paint adhesion.
  • FIGS. 17-20 show sealed cobalt conversion coating 270.
  • the cobalt conversion coating was formed on the substrate and then the coating was partially sealed by immersion in a sealing solution.
  • FIG. 18 shows the partially sealed structure of coating 270.
  • Sealed oxide coating 270 is not as porous as an unsealed oxide coating, the pores of the oxide coating being partially filled by hydration as a result of immersion in a sealing solution. The partial sealing of the oxide coating gives reduced paint adhesion results, but excellent corrosion resistance performance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Chemically Coating (AREA)
EP91202181A 1990-11-30 1991-08-27 Revêtement de conversion au cobalt, sans chromate Expired - Lifetime EP0488430B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US621132 1984-06-15
US62113290A 1990-11-30 1990-11-30

Publications (3)

Publication Number Publication Date
EP0488430A2 true EP0488430A2 (fr) 1992-06-03
EP0488430A3 EP0488430A3 (en) 1992-12-16
EP0488430B1 EP0488430B1 (fr) 1997-06-11

Family

ID=24488866

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91202181A Expired - Lifetime EP0488430B1 (fr) 1990-11-30 1991-08-27 Revêtement de conversion au cobalt, sans chromate

Country Status (13)

Country Link
EP (1) EP0488430B1 (fr)
JP (1) JP3194607B2 (fr)
AT (1) ATE154401T1 (fr)
AU (1) AU650494B2 (fr)
BR (1) BR9105184A (fr)
CA (1) CA2056159C (fr)
DE (1) DE69126507T2 (fr)
DK (1) DK0488430T3 (fr)
ES (1) ES2104655T3 (fr)
GR (1) GR3024046T3 (fr)
HK (1) HK1006861A1 (fr)
MX (1) MX9102254A (fr)
NZ (1) NZ240779A (fr)

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0523288A1 (fr) * 1991-07-19 1993-01-20 The Boeing Company Revêtement d'oxyde non-chromaté pour des substrats en aluminium
WO1994000619A1 (fr) * 1992-06-25 1994-01-06 The Boeing Company Couche d'oxyde non chromate pour substrats en aluminium
US5298092A (en) * 1990-05-17 1994-03-29 The Boeing Company Non-chromated oxide coating for aluminum substrates
US5378293A (en) * 1990-05-17 1995-01-03 The Boeing Company Non-chromated oxide coating for aluminum substrates
US5411606A (en) * 1990-05-17 1995-05-02 The Boeing Company Non-chromated oxide coating for aluminum substrates
US5468307A (en) * 1990-05-17 1995-11-21 Schriever; Matthias P. Non-chromated oxide coating for aluminum substrates
US5472524A (en) * 1990-05-17 1995-12-05 The Boeing Company Non-chromated cobalt conversion coating method and coated articles
WO1996005335A1 (fr) * 1994-08-09 1996-02-22 The Boeing Company Revetement ameliore a base d'oxyde pour des substrats en aluminium, realise sans utilisation de chrome
EP0826792A1 (fr) * 1996-09-02 1998-03-04 Cfpi Industries Bain et procédé de phosphatation de substrats métalliques, concentré pour la préparation de ce bain et substrats métalliques traités à l'aide de ce procédé
US5843617A (en) * 1996-08-20 1998-12-01 Minnesota Mining & Manufacturing Company Thermal bleaching of infrared dyes
US5873953A (en) * 1996-12-26 1999-02-23 The Boeing Company Non-chromated oxide coating for aluminum substrates
US6022425A (en) * 1994-06-10 2000-02-08 Commonwealth Scientific And Industrial Research Organisation Conversion coating and process and solution for its formation
EP1009867A1 (fr) * 1997-05-16 2000-06-21 Henkel Corporation Composition d'etancheite renfermant du lithium et du vanadium et procede correspondant
US6206982B1 (en) 1994-11-11 2001-03-27 Commonwealth Scientific And Industrial Research Organisation Process and solution for providing a conversion coating on a metal surface
US6315823B1 (en) 1998-05-15 2001-11-13 Henkel Corporation Lithium and vanadium containing sealing composition and process therewith
US6503565B1 (en) 1993-09-13 2003-01-07 Commonwealth Scientific And Industrial Research Organisation Metal treatment with acidic, rare earth ion containing cleaning solution
WO2003060191A2 (fr) * 2002-01-04 2003-07-24 University Of Dayton Revetements de conversion anti-corrosion non toxiques a base de cobalt
US6755917B2 (en) 2000-03-20 2004-06-29 Commonwealth Scientific And Industrial Research Organisation Process and solution for providing a conversion coating on a metallic surface II
US6773516B2 (en) 2000-03-20 2004-08-10 Commonwealth Scientific And Industrial Research Organisation Process and solution for providing a conversion coating on a metallic surface I
US7235142B2 (en) 2002-01-04 2007-06-26 University Of Dayton Non-toxic corrosion-protection rinses and seals based on cobalt
US7291217B2 (en) 2002-01-04 2007-11-06 University Of Dayton Non-toxic corrosion-protection pigments based on rare earth elements
US7537663B2 (en) 2002-07-24 2009-05-26 University Of Dayton Corrosion-inhibiting coating
US7789958B2 (en) 2003-01-13 2010-09-07 University Of Dayton Non-toxic corrosion-protection pigments based on manganese

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6432225B1 (en) * 1999-11-02 2002-08-13 The Boeing Company Non-chromated oxide coating for aluminum substrates
JP4934984B2 (ja) * 2005-03-31 2012-05-23 大日本印刷株式会社 金属酸化物膜の製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3905838A (en) * 1974-04-10 1975-09-16 Hikaru Ito Bath for treating aluminum and aluminum alloys to form oxide film nonelectrolytically thereon and method for the treatment
US4381203A (en) * 1981-11-27 1983-04-26 Amchem Products, Inc. Coating solutions for zinc surfaces
EP0405340A1 (fr) * 1989-06-27 1991-01-02 Henkel Corporation Traitement de surface noircissant pour surfaces contenant du zinc
WO1991011542A2 (fr) * 1990-01-30 1991-08-08 Henkel Corporation Procede et composition de traitement de surface pour tole galvanisee
EP0458020A1 (fr) * 1990-05-17 1991-11-27 The Boeing Company Revêtement d'oxyde sans chromate pour substrats en aluminium

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3905838A (en) * 1974-04-10 1975-09-16 Hikaru Ito Bath for treating aluminum and aluminum alloys to form oxide film nonelectrolytically thereon and method for the treatment
US4381203A (en) * 1981-11-27 1983-04-26 Amchem Products, Inc. Coating solutions for zinc surfaces
EP0405340A1 (fr) * 1989-06-27 1991-01-02 Henkel Corporation Traitement de surface noircissant pour surfaces contenant du zinc
WO1991011542A2 (fr) * 1990-01-30 1991-08-08 Henkel Corporation Procede et composition de traitement de surface pour tole galvanisee
EP0458020A1 (fr) * 1990-05-17 1991-11-27 The Boeing Company Revêtement d'oxyde sans chromate pour substrats en aluminium

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PASCAL 'Nouveau Traité de Chimie Minérale' 1959 , MASSON & CIE , PARIS,FR Volume XVIII, Pages 680-681 : COBALTINITRITES *

Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5468307A (en) * 1990-05-17 1995-11-21 Schriever; Matthias P. Non-chromated oxide coating for aluminum substrates
US5472524A (en) * 1990-05-17 1995-12-05 The Boeing Company Non-chromated cobalt conversion coating method and coated articles
US5298092A (en) * 1990-05-17 1994-03-29 The Boeing Company Non-chromated oxide coating for aluminum substrates
US5378293A (en) * 1990-05-17 1995-01-03 The Boeing Company Non-chromated oxide coating for aluminum substrates
US5411606A (en) * 1990-05-17 1995-05-02 The Boeing Company Non-chromated oxide coating for aluminum substrates
US5415687A (en) * 1990-05-17 1995-05-16 The Boeing Company Non-chromated oxide coating for aluminum substrates
US5551994A (en) * 1990-05-17 1996-09-03 The Boeing Company Non-chromated oxide coating for aluminum substrates
EP0523288A1 (fr) * 1991-07-19 1993-01-20 The Boeing Company Revêtement d'oxyde non-chromaté pour des substrats en aluminium
WO1994000619A1 (fr) * 1992-06-25 1994-01-06 The Boeing Company Couche d'oxyde non chromate pour substrats en aluminium
AU687740B2 (en) * 1992-06-25 1998-03-05 Boeing Company, The Non-chromated oxide coating for aluminum substrates
US6503565B1 (en) 1993-09-13 2003-01-07 Commonwealth Scientific And Industrial Research Organisation Metal treatment with acidic, rare earth ion containing cleaning solution
US6022425A (en) * 1994-06-10 2000-02-08 Commonwealth Scientific And Industrial Research Organisation Conversion coating and process and solution for its formation
WO1996005335A1 (fr) * 1994-08-09 1996-02-22 The Boeing Company Revetement ameliore a base d'oxyde pour des substrats en aluminium, realise sans utilisation de chrome
US6206982B1 (en) 1994-11-11 2001-03-27 Commonwealth Scientific And Industrial Research Organisation Process and solution for providing a conversion coating on a metal surface
US5843617A (en) * 1996-08-20 1998-12-01 Minnesota Mining & Manufacturing Company Thermal bleaching of infrared dyes
US6068709A (en) * 1996-09-02 2000-05-30 Cfpi Industries Bath and process for the phosphatization of metallic substrates, concentrates for the preparation of said bath and metallic substrates having been subjected to a treatment by said bath and process
FR2752851A1 (fr) * 1996-09-02 1998-03-06 Cfpi Ind Bain et procede de phosphatation de substrats metalliques, concentre pour la preparation de ce bain et substrats metalliques traites a l'aide de ces bain et procede
EP0826792A1 (fr) * 1996-09-02 1998-03-04 Cfpi Industries Bain et procédé de phosphatation de substrats métalliques, concentré pour la préparation de ce bain et substrats métalliques traités à l'aide de ce procédé
US5873953A (en) * 1996-12-26 1999-02-23 The Boeing Company Non-chromated oxide coating for aluminum substrates
EP1009867A1 (fr) * 1997-05-16 2000-06-21 Henkel Corporation Composition d'etancheite renfermant du lithium et du vanadium et procede correspondant
EP1009867A4 (fr) * 1997-05-16 2000-08-09 Henkel Corp Composition d'etancheite renfermant du lithium et du vanadium et procede correspondant
US6315823B1 (en) 1998-05-15 2001-11-13 Henkel Corporation Lithium and vanadium containing sealing composition and process therewith
US6755917B2 (en) 2000-03-20 2004-06-29 Commonwealth Scientific And Industrial Research Organisation Process and solution for providing a conversion coating on a metallic surface II
US6773516B2 (en) 2000-03-20 2004-08-10 Commonwealth Scientific And Industrial Research Organisation Process and solution for providing a conversion coating on a metallic surface I
WO2003060191A3 (fr) * 2002-01-04 2003-12-18 Univ Dayton Revetements de conversion anti-corrosion non toxiques a base de cobalt
WO2003060191A2 (fr) * 2002-01-04 2003-07-24 University Of Dayton Revetements de conversion anti-corrosion non toxiques a base de cobalt
US7235142B2 (en) 2002-01-04 2007-06-26 University Of Dayton Non-toxic corrosion-protection rinses and seals based on cobalt
US7291217B2 (en) 2002-01-04 2007-11-06 University Of Dayton Non-toxic corrosion-protection pigments based on rare earth elements
US7294211B2 (en) 2002-01-04 2007-11-13 University Of Dayton Non-toxic corrosion-protection conversion coats based on cobalt
US7407711B2 (en) 2002-01-04 2008-08-05 University Of Dayton Non-toxic corrosion-protection conversion coats based on rare earth elements
US7422793B2 (en) 2002-01-04 2008-09-09 University Of Dayton Non-toxic corrosion-protection rinses and seals based on rare earth elements
US7833331B2 (en) 2002-01-04 2010-11-16 University Of Dayton Non-toxic corrosion-protection pigments based on cobalt
US7537663B2 (en) 2002-07-24 2009-05-26 University Of Dayton Corrosion-inhibiting coating
US7789958B2 (en) 2003-01-13 2010-09-07 University Of Dayton Non-toxic corrosion-protection pigments based on manganese

Also Published As

Publication number Publication date
ES2104655T3 (es) 1997-10-16
CA2056159C (fr) 2001-07-03
CA2056159A1 (fr) 1992-05-31
JPH059745A (ja) 1993-01-19
GR3024046T3 (en) 1997-10-31
DE69126507T2 (de) 1997-09-25
AU8822591A (en) 1992-06-04
HK1006861A1 (en) 1999-03-19
EP0488430A3 (en) 1992-12-16
NZ240779A (en) 1994-11-25
DK0488430T3 (da) 1998-01-05
EP0488430B1 (fr) 1997-06-11
DE69126507D1 (de) 1997-07-17
ATE154401T1 (de) 1997-06-15
AU650494B2 (en) 1994-06-23
MX9102254A (es) 1992-06-01
BR9105184A (pt) 1992-07-21
JP3194607B2 (ja) 2001-07-30

Similar Documents

Publication Publication Date Title
EP0488430A2 (fr) Revêtement de conversion au cobalt, sans chromate
EP0458020B1 (fr) Revêtement d'oxyde sans chromate pour substrats en aluminium
EP0776384B1 (fr) Revetement ameliore a base d'oxyde pour des substrats en aluminium, realise sans utilisation de chrome
US5472524A (en) Non-chromated cobalt conversion coating method and coated articles
EP0646187B1 (fr) Couche d'oxyde non chromate pour substrats en aluminium
US5411606A (en) Non-chromated oxide coating for aluminum substrates
US5873953A (en) Non-chromated oxide coating for aluminum substrates
EP0523288B1 (fr) Revêtement d'oxyde non-chromaté pour des substrats en aluminium
US5378293A (en) Non-chromated oxide coating for aluminum substrates
EP1230424B1 (fr) Couche d'oxyde non chromatee pour substrats en aluminium
US5468307A (en) Non-chromated oxide coating for aluminum substrates
KR100305009B1 (ko) 알루미늄기판을위한비-크롬산염산화물코팅을형성하는방법
KR100327142B1 (ko) 금속기재상에코발트전환코팅을형성하기위한방법및화학전환코팅용액및상기방법으로제조한물품
RU2130977C1 (ru) Способ формирования оксидного кобальтового конверсионного покрытия и водный химический раствор для получения оксидного кобальтового конверсионного покрытия
NZ245684A (en) Solution and process for producing a cobalt conversion coating on a metal substrate
NO310154B1 (no) Fremgangsmåte ved fremstilling av et korrosjonsresistent og adhesjonsfremmende belegg på et substrat, samt vandig kjemisk badfor anvendelse i fremgangsmåten

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

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19930615

17Q First examination report despatched

Effective date: 19930719

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

REF Corresponds to:

Ref document number: 154401

Country of ref document: AT

Date of ref document: 19970615

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: ARNOLD & SIEDSMA AG

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 69126507

Country of ref document: DE

Date of ref document: 19970717

REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3024046

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2104655

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

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

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

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

Ref country code: CH

Payment date: 20100812

Year of fee payment: 20

Ref country code: ES

Payment date: 20100915

Year of fee payment: 20

Ref country code: NL

Payment date: 20100810

Year of fee payment: 20

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

Ref country code: SE

Payment date: 20100812

Year of fee payment: 20

Ref country code: LU

Payment date: 20100915

Year of fee payment: 20

Ref country code: IT

Payment date: 20100823

Year of fee payment: 20

Ref country code: FR

Payment date: 20100824

Year of fee payment: 20

Ref country code: DE

Payment date: 20100825

Year of fee payment: 20

Ref country code: AT

Payment date: 20100812

Year of fee payment: 20

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

Ref country code: GR

Payment date: 20100719

Year of fee payment: 20

Ref country code: GB

Payment date: 20100825

Year of fee payment: 20

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

Ref country code: DK

Payment date: 20100812

Year of fee payment: 20

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

Ref country code: BE

Payment date: 20100818

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69126507

Country of ref document: DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69126507

Country of ref document: DE

BE20 Be: patent expired

Owner name: THE *BOEING CY

Effective date: 20110827

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: NL

Ref legal event code: V4

Effective date: 20110827

REG Reference to a national code

Ref country code: DK

Ref legal event code: EUP

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20110826

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

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

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20110826

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 EXPIRATION OF PROTECTION

Effective date: 20110827

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20120110

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 EXPIRATION OF PROTECTION

Effective date: 20110828

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 EXPIRATION OF PROTECTION

Effective date: 20110828