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WO1996021753A1 - Composition et procede destine a former un revetement protecteur adherent solide sur des surfaces en metal - Google Patents

Composition et procede destine a former un revetement protecteur adherent solide sur des surfaces en metal Download PDF

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Publication number
WO1996021753A1
WO1996021753A1 PCT/US1995/000205 US9500205W WO9621753A1 WO 1996021753 A1 WO1996021753 A1 WO 1996021753A1 US 9500205 W US9500205 W US 9500205W WO 9621753 A1 WO9621753 A1 WO 9621753A1
Authority
WO
WIPO (PCT)
Prior art keywords
cobalt
molar concentration
cations
composition according
aqueous liquid
Prior art date
Application number
PCT/US1995/000205
Other languages
English (en)
Inventor
Shawn E. Dolan
Lawrence R. Carlson
John R. Pierce
Original Assignee
Henkel Corporation
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 Henkel Corporation filed Critical Henkel Corporation
Priority to PCT/US1995/000205 priority Critical patent/WO1996021753A1/fr
Priority to US08/454,301 priority patent/US5948178A/en
Publication of WO1996021753A1 publication Critical patent/WO1996021753A1/fr
Priority to US09/200,526 priority patent/US5993567A/en

Links

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
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/56—Treatment of aluminium or alloys based thereon
    • 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 compositions and processes for forming a protective coating on metal, particularly aluminum and/or aluminum alloy, surfaces.
  • the coating formed is solid and adherent, often although not always colored, provides good corrosion protection to the metal surface, and functions as an excellent base for painting or similar organic based protective coatings.
  • the coatings formed, when applied to substrates of aluminum and its alloys, usually impart as much corrosion protection as do conventional coatings formed by use of hexavalent chromium containing compositions, but the compo- sitions and processes according to this invention cause less potential environmental dam ⁇ age because they do not need hexavalent chromium or other identified major pollutants. Discussion of Related Art
  • compositions taught in this related art although they have avoided the use of hexavalent chromium and other pollutants of the general environment, never ⁇ theless can have adverse environmental impacts on the immediate working area for the process and any workers in this area.
  • many of the formulations previously used include high concentrations of ammonia, which causes at least a severe odor nui- sance and possibly a serious health hazard to workers in the vicinity, unless expensive ventilation equipment is installed in the process area.
  • concentration of ammonia in aqueous solutions is difficult to maintain constant, as is desirable for achiev ⁇ ing the most consistent results from the process, at the high levels previously recom ⁇ mended by some related art.
  • One major object of the invention is to provide compositions and processes that have reduced adverse environmental impact compared with related previously recom ⁇ mended processes as described above.
  • Another alternative object is to provide more eco ⁇ nomical compositions and processes than those previously recommended, in particular by at least one of the following means: (i) reducing the treatment time required to form an effective protective coating and (ii) lowering the concentrations of active ingredients.
  • Still another alternative object is to provide coatings with higher corrosion resistance, as formed and/or after subsequent painting or the like.
  • percent, "parts of, and ratio values are by weight;
  • the term "polymer” includes oligomer;
  • the description of a group or class of materials as suitable or preferred for a given purpose in connection with the invention implies that mixtures of any two or more of the members of the group or class are equally suitable or preferred;
  • description of constituents in chemical terms refers to the constituents at the time of addition to any combination specified in the de ⁇ scription, and does not necessarily preclude chemical interactions among the constituents of a mixture once mixed;
  • specification of materials in ionic form implies the presence of sufficient counterions to produce electrical neutrality for the composition as a whole (any counterions thus implicitly specified should preferably be selected from among other constituents explicitly specified in ionic form, to the extent possible; otherwise such counterions may be freely selected, except for avoiding counterions that act adversely to the stated objects of the invention); and the term "mole” and its variations may be ap ⁇ plied to elemental, ionic, and any other chemical species defined by number and type
  • compositions according to the invention are made by reaction in an aqueous solution comprising, preferably consisting essentially of, or more preferably consisting of, water and the following dissolved components: (A) cobalt(II) cations;
  • Various embodiments of the invention include working compositions for direct use in treating metals, concentrates from which such working compositions can be. pre ⁇ pared by dilution with water and/or mixing w h other concentrates, processes for treating metals with a composition according to the invention, and extended processes including additional steps that are conventional per se, such as precleaning, rinsing, and, particular ⁇ ly advantageously, painting or some similar overcoating process that puts into place a protective coating containing an organic binder over the conversion coating formed ac ⁇ cording to a narrower embodiment of the invention.
  • Articles of manufacture including surfaces treated according to a process of the invention are also within the scope of the invention.
  • compositions according to the inven ⁇ tion as defined above should be substantially free from many ingredients used in compo ⁇ sitions for similar purposes in the prior art.
  • these compositions when directly contacted with metal in a process according to this invention, contain no more than 1.0, 0.35, 0.10, 0.08, 0.04, 0.02, 0.01, 0.001, or 0.0002, percent of each of the following constituents: hexavalent chromium, cyanide, nitrite ions, ammonia and ammonium cations, and any coordinate complexing agents that stabilize cobalt( ⁇ ) more than cobalt(III) cations.
  • a process according to the invention that includes other steps than the drying into place on the surface of the metal of a layer of a composition as described above, it is preferred that none of these other steps include contacting the surfaces with any composition that contains more than, with increasing preference in the order given, 1.0, 0.35, 0.10, 0.08, 0.04, 0.02, 0.01, 0.003, 0.001, or 0.0002 % of hexavalent chromium, except that a final protective coating system including an organic binder, more particular- ly those including primer coat, may include hexavalent chromium as a constituent. Any such hexavalent chromium in the protective coating is generally adequately confined by the organic binder, so as to avoid adverse environmental impact.
  • the concentration of component (A) reacted preferably is such that, in a working composition according to the invention, the concentration of cobalt atoms is, with in- creasing preference in the order given, not less than 0.001, 0.002, 0.004, 0.008, 0.016,
  • M moles per liter
  • M moles per liter
  • M moles per liter
  • the particular counterion(s) in the salt(s) in the form of which the cobalt cations are actually added to the aqueous solution in which they are reacted are not believed to be critical, except for avoiding any counterions that bind so stably to cobalt(II) that they prevent it from being oxidized to cobalt(III) during re ⁇ action with the other components.
  • the counterions for cobalt when added to the aqueous solution in which it is reacted are preferably selected from the group consisting of nitrate ions, which have relatively weak complex forming tendencies, and carboxylate ions that are part of component (B).
  • Component (B) is preferably selected from the anions of unsubstituted carboxylic acids containing from 1 to 6 carbon atoms, or more preferably, with increasing prefer- ence in the order given, not more than 5, 4, 3, or 2 carbon atoms, per molecule.
  • Acetate ions are most preferred, largely because they are less expensive than most other carbox- ylates.
  • the ratio of the number of moles of component (B) to the number of moles of component (A) in solution before any reaction between them preferably is, with increasing preference in the order given, at least 0.1 , 0.2, 0.4, 0.8, 1.2, 1.5, 1.8, 2.0, 2.2, 2.3, 2.4, 2.5, or 2.6 and independently preferably is, with increasing preference in the order given, not greater than 6.5, 6.0, 5.5, 5.0, 4.5, 4.0, 3.7, 3.4, 3.1, 3.0, 2.9, 2.8, or 2.7.
  • carboxylate ions are thus greater than can be supplied by cobalt(II) carboxylates themselves, and for the alternative cations that serve as counterions for this "excess" carboxylate, alkaline earth metal cations, particularly magnesium and calcium, most preferably magnesium, are preferred over alkali metal cat ⁇ ions, although the latter can also be used.
  • alkaline earth metal cations particularly magnesium and calcium, most preferably magnesium, are preferred over alkali metal cat ⁇ ions, although the latter can also be used.
  • carboxylic acids to supply the need- ed amounts of carboxylate ions although also possible within the scope of the invention, is not preferred, because such use tends to depress the pH range below the most preferred values as set forth below.
  • Component (C) preferably is selected from organic compounds containing at least one nitrogen or phosphorus atom, more preferably nitrogen atom, with an unshared electron pair per molecule of compound.
  • Hydroxyalkyl amines most particularly triethanol amine, are the most preferred class of materials for component (C).
  • the ratio of molar concentration of the total of nitrogen and phosphorus atoms each bearing an unshared electron pair to the molar concentration of component (A) present in solution before any reaction between them preferably is, with increasing preference in the order given, not less than 0.03, 0.06, 0.13, 0.20, 0.24, 0.26, 0.28, 0.30,
  • 0.32, 0.34, 0.35, or 0.36 independently preferably is, with increasing preference in the order given, not more than 2.0, 1.75, 1.50, 1.25, 1.00, 0.75, 0.60, 0.50, 0.45, 0.41, 0.39, or 0.38.
  • the amount and oxidizing strength of component (D) used should be sufficient to cause a change in the color and/or an increase in the ultraviolet adsorption at some wavelength in the range of 160 - 450 nanometers (hereinafter abbreviated "nm") of a pre ⁇ cursor solution containing only water, components (A), (B), and (C), and any possible reaction products among these constituents, after component (D) is added to the precur ⁇ sor mixture solution.
  • soluble compounds including a peroxide and or superoxide moiety are preferred, with peroxide more preferred and hydrogen peroxide most preferred, as at least part of component (D).
  • the ratio of the molar concentration of peroxide moieties present in the solution before reaction to the molar concentration of cobalt atoms present in the solution preferably is, with increasing preference in the order given, at least 0.05, 0.10, 0.20, 0.30, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.68, 0.71, or 0.73 and independently prefer- ably is, with increasing preference in the order given, not more than 10, 7, 5, 3, 2, 1.5, 1.0, 0.95, 0.90, 0.85, 0.80, 0.77, or 0.74.
  • compositions according to the invention it is preferable to keep the composition well aerated during use, by employing (i) a spray to contact the solution with the metal to be treated, (ii) a separate spray treater for aeration purposes in a process line through which the composition according to the invention is circulated during use, and/or (iii) sparging with air and/or oxygen gas in a container for the composition in such a process line, which container conveniently may be the immersion tank if immersion processing is used.
  • the ratio of the molar concentration of nitrate ions before reaction to the molar concentration of cobalt atoms in the aqueous compositions reacted to make compositions according to this invention preferably is, with increasing preference in the order given, not less than 0.05,
  • the pH value of working compositions according to this invention preferably is, with increasing preference in the order given, at least 3, 4, 4.5, 5.0, 5.5, 6.0, 6.2, 6.3, 6.4,
  • 6.5, 6.6, 6.7, or 6.8 and independently preferably is, with increasing preference in the order given, not more than 10, 9, 8.5, 8.2, 8.0, 7.9, 7.8, 7.7, 7.6, 7.5, 7.4, 7.3, or 7.2.
  • Val ⁇ ues of pH within these preferred ranges will generally result from using the preferred components noted above in preparing the compositions according to the invention, but the pH value may be adjusted as needed by minor additions of other acidic or basic com ⁇ ponents as generally known in the art.
  • components (A) and (B) are preferably mixed together in aqueous solution at first in the absence of other con ⁇ stituents, except for the counterions of components (A) and (B), and component (C) then added to this mixture. Only after components (A), (B), and (C) have been well mixed in solution should any component (D) (except for the air in equilibrium with the aqueous solution) be added.
  • any component (D) except for the air in equilibrium with the aqueous solution.
  • the temperature during mixing is not believed to be critic- al, so that any temperature between the freezing and boiling points of the solution may be used, all these additions are most preferably made while the solution is at approxi ⁇ mately normal ambient temperature, i.e., 20 - 25 ° C.
  • a preferred partial concentrate composition according to the invention is an aque ⁇ ous liquid composition that consists essentially of, or more preferably consists of, water, cobalt( ⁇ ) cations, carboxylate anions, and any additional counterions needed for the lat ⁇ ter two constituents.
  • These partial concentrates preferably contain, with increasing pref ⁇ erence in the order given, at least 1, 2.0, 2.5, 3.0, 3.3. 3.5, or 3.7 % of cobalt(II) cations and independently preferably have molar ratios of carboxylate and cobalt(II) within the same preferred ranges as are indicated above for working compositions according to the invention. More preferably, the only essential constituents of these concentrates are water, cobalt nitrate, and alkaline earth metal, most preferably magnesium, acetate.
  • a metal substrate surface preferably should be cleaned and, if the substrate is one of the metals such as aluminum and magnesium that are prone to spontaneous formation of thick oxide layers on their surfaces, deoxidized by processes known per se in the prior art, or other suitable processes. Preferred examples may be found in the working examp ⁇ les below.
  • compositions according to the invention can be used in processes according to the invention over a substantial range of temperatures, with formation of protective coat- ings generally at least slightly faster at higher temperatures within the range.
  • the temperature during contact between a composition according to the inven ⁇ tion and a metal substrate to be treated preferably is, with increasing preference in the order given, at least 20, 30, 35, 40, 43, 45, 47, or 49 ° C and independently preferably is, with increasing preference in the order given, not more than 90, 85, 80, 75, 72, 69, 67, 65, 63, 62, 61, or 60 ° C.
  • Contact between a composition according to the invention and the metal substrate s being treated in a process according to the invention can be achieved by any convenient method or combination of methods.
  • Immersion and spraying for example, are both cap ⁇ able of giving completely satisfactory results.
  • spraying achieves desired coat ⁇ ing weights somewhat more rapidly than immersion, perhaps because of more effective mixing of the portion of the liquid composition in close proximity to the treated surface o with the bulk of the liquid composition and/or the greater opportunity for atmospheric oxygen to participate in the coating forming reaction that is provided by spraying.
  • the contact time preferably is, with increasing preference in the order given, not less than 5, 10, 20, 30, 40, 50, 60, 65, 70, 75, 80, 85, or 90 seconds (hereinafter usually abbreviated "sec") and independently preferably is, s with increasing preference in the order given, not more than 30, 15, 12, 10, 8, 6, 5, 4, 3,
  • the contact time preferably is, with increasing preference in the order given, at least 0.2, 0.5, 0.8, 1.0, 1.5, 2.0, 2.5, 2.8, 3.2, 3.6, or 3.9 min and independently preferably is, with increasing preference in the order given, not more than 30, 25, 20, 15, 0 12, 9, 8, 7, 6, or 5 min.
  • the treated metal surface now bearing a protective coating formed according to the invention preferably is rinsed with water before being dried or allowed to dry.
  • the protective value of the coating can be further enhanced by a "sealing" treatment 5 with another composition.
  • One preferred sealing treatment composition denoted herein ⁇ after as “Inorganic Sealing Treatment Composition #1" is an aqueous solution made by reacting 3.0 grams per liter (hereinafter usually abbreviated "g L") of dispersed finely di ⁇ vided vanadium pentoxide, 10.0 g/L of sodium tungstate, and 3.0 g/L of hydrogen perox ⁇ ide together in water.
  • a second preferred sealing treatment composition contains the following ingred ⁇ ients: 0.9 % of 45 % fluozircoriic acid, 1.07 % of 67 % nitric acid, 0.48 % of 75 % ortho- phosphoric acid, and 22.6 % of an aqueous solution containing 30.4 % solids of a water soluble glucamino-substituted polymer of vinyl phenol made according to the directions of column 11 lines 39 - 52 of U. S. Patent 4,963,596, with the balance being deionized or otherwise purified water, plus any aqueous ammonia needed to adjust the pH of the sealing treatment composition to 4.0.
  • Other suitable sealing treatment compositions are taught in U. S. Patent 5,226,976.
  • the treated metal surfaces preferably are again rinsed before drying or being allowed to dry. If heat is used to accelerate drying, the temperature of the metal during drying preferably does not exceed, with increasing pre ⁇ ference in the order given, 100, 85, 75, 66, or 60 ° C, in order to avoid damage to the pro- tective quality of the coating formed by a process according to the invention
  • a metal substrate is well suited as a base for paint or any similar organic based protective coating, which may be applied in any manner known pe se in the art.
  • Example 1 The invention may be further appreciated by consideration of the following non- limiting working examples.
  • Example 1 The invention may be further appreciated by consideration of the following non- limiting working examples.
  • a working composition according to the invention was prepared as follows: 1063 grams of an aqueous solution of cobalt(II) nitrate containing 13 % of cobalt and 670 grams of magnesium acetate tetrahydrate were added to about 15 liters of deionized wat- er. After these ingredients had been thoroughly mixed at ambient temperature, aeration of the liquid mixture was begun, 131 grams of triethanolamine of 99 % purity was added, and after thorough mixing of this ingredient had been accomplished, 168 grams of an aqueous solution of hydrogen peroxide containing 35 % H 2 O 2 was added.
  • This liquid mixture was then diluted to a total volume of 30.3 liters with additional deionized water, to produce a liquid solution according to the invention that, when diluted to 10 times its initial volume with deionized water produces a test liquid with an absorbance of UV light at 362 nm wavelength, over a 1 cm long transmission path, in the range from 4 to 40 %.
  • Heating of the liquid was begun, and aeration was continued until the temperature of the mixture had been raised to 54 ⁇ 1 ⁇ C, the selected working temperature, which was maintained during use of the composition as described below.
  • Rectangular panels of Type 2024-T3 aluminum alloy that were 7.6 * 25.4 centi ⁇ meters in size were the substrates used. These substrates were subjected to the following process steps, in which all products identified by trademarks are available from the Par ⁇ ker Amchem Division of Henkel Corp., Madison Heights, Michigan: 1. Clean by immersion for 5 min at 60° C in an aqueous solution containing 15 g/L of RIDOLINE® 53 silicate inhibited alkaline cleaner. 2. Rinse with hot water.
  • step 10 The panels not subjected to step 10 above were tested in standard salt spray for one week and exhibited no pits or discoloration.
  • the panels subjected to step 10 were scribed and then tested in standard salt spray. No creepage away from the scribe was de- tectable after 1000 hours of salt spray exposure.
  • Example 2
  • the substrates in this example were made of aluminum casting alloy. They were subjected to the following process steps, in which all products identified by trademarks are available from the Parker Amchem Division of Henkel Corp., Madison Heights, Michigan:

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  • 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)
  • Paints Or Removers (AREA)

Abstract

On fabrique une composition aqueuse liquide sans chromate destinée à former un revêtement protecteur sur les métaux, notamment l'aluminium, en faisant réagir des cations cobalt (II), des anions carboxylate, au minimum un autre type d'agent complexant de coordination pour des cations cobalt (III) et un agent oxydant dans une solution aqueuse dans laquelle le rapport molaire entre les anions carboxylate et les cations cobalt (II) est de 0,10 pour 6,8; la solution aqueuse ne contenant pas plus de 1 % d'ammoniac, d'ions ammonium et d'ions nitrite.
PCT/US1995/000205 1995-01-13 1995-01-13 Composition et procede destine a former un revetement protecteur adherent solide sur des surfaces en metal WO1996021753A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
PCT/US1995/000205 WO1996021753A1 (fr) 1995-01-13 1995-01-13 Composition et procede destine a former un revetement protecteur adherent solide sur des surfaces en metal
US08/454,301 US5948178A (en) 1995-01-13 1995-01-13 Composition and process for forming a solid adherent protective coating on metal surfaces
US09/200,526 US5993567A (en) 1995-01-13 1998-11-25 Compositions and processes for forming a solid adherent protective coating on metal surfaces

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1995/000205 WO1996021753A1 (fr) 1995-01-13 1995-01-13 Composition et procede destine a former un revetement protecteur adherent solide sur des surfaces en metal

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US41223395A Continuation-In-Part 1995-01-13 1995-03-22

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Publication Number Publication Date
WO1996021753A1 true WO1996021753A1 (fr) 1996-07-18

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0815286A4 (fr) * 1995-03-22 1998-05-06 Henkel Corp Compositions et procedes de realisation d'un revetement protecteur adherant solide sur des surfaces metalliques
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
WO2003060191A3 (fr) * 2002-01-04 2003-12-18 Univ 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

Citations (3)

* 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
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

Patent Citations (3)

* 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
US5298092A (en) * 1990-05-17 1994-03-29 The Boeing Company Non-chromated oxide coating for aluminum substrates
WO1994000619A1 (fr) * 1992-06-25 1994-01-06 The Boeing Company Couche d'oxyde non chromate pour substrats en aluminium

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0815286A4 (fr) * 1995-03-22 1998-05-06 Henkel Corp Compositions et procedes de realisation d'un revetement protecteur adherant solide sur des surfaces metalliques
US5843242A (en) * 1995-03-22 1998-12-01 Henkel Corporation Compositions and processes for forming a solid adherent protective coating on metal surfaces
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
WO2003060191A3 (fr) * 2002-01-04 2003-12-18 Univ 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

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