EP2766508B1 - Verfahren zur korrosionsschutzbehandlung fester metallsubstrate - Google Patents

Verfahren zur korrosionsschutzbehandlung fester metallsubstrate Download PDF

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Publication number
EP2766508B1
EP2766508B1 EP12781391.3A EP12781391A EP2766508B1 EP 2766508 B1 EP2766508 B1 EP 2766508B1 EP 12781391 A EP12781391 A EP 12781391A EP 2766508 B1 EP2766508 B1 EP 2766508B1
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Prior art keywords
metal substrate
solid metal
solution
treatment solution
cerium
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French (fr)
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EP2766508A1 (de
Inventor
Florence Ansart
Rudina BLETA
Jean-Pierre Bonino
Julien ESTEBAN
Olivier JAUBERT
Marie GRESSIER
Pascal Lenormand
Marie-Joëlle MENU
Elodie XUEREB
Pierre Bares
Céline GAZEAU
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Centre National de la Recherche Scientifique CNRS
Universite Toulouse III Paul Sabatier
Mecaprotec Industries SA
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Centre National de la Recherche Scientifique CNRS
Universite Toulouse III Paul Sabatier
Mecaprotec Industries SA
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    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/04—Pretreatment of the material to be coated
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/122—Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

Definitions

  • the invention relates to a method for anticorrosion treatment of a solid metal substrate, in particular an aluminum or aluminum alloy substrate.
  • the invention further relates to a corrosion-resistant solid metal substrate obtainable by such a method.
  • Such an anticorrosion treatment method has applications in the general field of surface treatment of solid metal substrates, in particular metal parts.
  • Such a method has its applications in the field of transport vehicles, including ships, motor vehicles and aircraft in which the problem of the fight against corrosion of metal parts arises.
  • the invention aims to overcome the disadvantages mentioned above by proposing a method of anticorrosion treatment of a solid metal substrate that does not require the use of chromium derivatives-especially chromium VI- which is carcinogenic, mutagenic and reprotoxic.
  • the object of the invention is to provide an anticorrosive treatment method adapted to form a corrosion-resistant coating on the surface of a solid metal substrate which is of high mechanical strength.
  • the invention also aims at providing such an anticorrosion treatment method which makes it possible to obtain a layer of anticorrosion coating of controlled thickness, in particular between 1 ⁇ m and 15 ⁇ m, and compatible with the industrial recommendations, particularly in the field. aeronautics.
  • Another objective of the invention is to propose a method for the anticorrosion treatment of a solid metal substrate - particularly metallic parts for aeronautics - adapted to allow the formation of an anticorrosion coating of said solid metal substrate which is of thickness substantially homogeneous on the surface of the solid metal substrate, which is covering and which is also leveling.
  • leveling it is meant that such a coating has a free outer surface-that is, opposed to the substrate-which is substantially planar regardless of the presence of structural defects on the surface of the underlying solid metal substrate.
  • the invention aims to provide such a method adapted to allow the formation of an anticorrosion coating having no cracking at said structural defects.
  • the invention also aims at such a method which is adapted to allow the formation of an anticorrosion layer which is resistant to cracking.
  • the invention furthermore aims at such a method adapted to allow the formation of a surface anticorrosion coating of a solid metal substrate having at the same time passive protection properties - in particular, by barrier effect of said substrate vis-à- vis of an outside environment corrosive and protective active healing properties and limiting the progression of corrosion at an accidental bite likely to affect the anticorrosive coating.
  • the invention also aims at such an anticorrosion treatment method adapted to be applied on a polished solid metal substrate or on an unpolished solid metal substrate.
  • the invention also aims to achieve all these objectives at lower cost, by proposing a method which is simple and which requires for its implementation that steps of contacting a solid metal substrate and liquid solutions.
  • the invention also aims and more particularly to provide such a method that is compatible with the constraints of safety and respect for the environment.
  • the invention further aims to provide such a solution that preserves the work habits of staff, is easy to use, and imply for its implementation that little manipulation.
  • the invention also aims at such an anticorrosion treatment method using a treatment solution that is simple in its composition compared to liquid treatment solutions of the state of the art.
  • the invention therefore also relates to an anticorrosive coating having improved protective properties compared to anti-corrosion coatings of the state of the art, including anti-corrosion properties which are improved over time.
  • the invention relates to an anticorrosion treatment method according to claim 1.
  • the treatment solution having a molar ratio (Si / Ce) of silicon element of (the) alkoxysilane (s) relative to the (x) cation (s) of cerium (Ce) between 50 and 500, in particular between 80 and 250.
  • the cation (s) of cerium (Ce) present (s) a concentration of between 0.005 mol / L and 0.015 mol / L -notamment between 0.005 mol / L and 0.01 mol / L, preferably of the order of 0.010 mol / L- in the treatment solution.
  • At least one alkoxysilane and at least one cerium (Ce) cation are mixed in a liquid aqueous-alcoholic solution under conditions suitable for allowing hydrolysis / condensation of said at least one alkoxysilane and said at least one a cation of cerium (Ce), and said treatment solution is applied to the oxidizable surface of a solid metal substrate so as to form on the surface of the solid metal substrate, a hybrid matrix by hydrolysis / condensation of each alkoxysilane (s) and each cation of cerium (Ce).
  • each alkoxysilane (s) is carried out in the treatment solution in the presence of each cation (s) of cerium (Ce), said treatment solution having a ratio (Si / This molar element of silicon of (the) starting alkoxysilane (s) relative to the (x) cation (s) of cerium (Ce) starting between 50 and 500, in particular between 80 and 250.
  • the inventors have observed that the selection of a concentration value of the cerium cations in the treatment solution does not constitute an arbitrary selection of concentration, but on the contrary that this selection provides a surprising result, totally unpredictable, not described in FIG. state of the art and according to which the selected concentration of the cerium (Ce) cation in the solution for the corrosion treatment of a solid metal substrate at the same time allows (1) to obtain optimal adhesion of the surface treatment solution of the solid metal substrate, (2) the formation of a hybrid matrix of passive protection of said solid metal substrate by a barrier effect adapted to limit the formation of corrosion products of the solid metal substrate - in particular of a solid metal substrate having a puncture -, and (3) to form such a hybrid protection matrix having Physical resistance properties to mechanical stresses - including resistance to delamination, crack resistance, and plastic deformation and corrosion resistance - at 1 day, 7 days and 14 days corrosive treatment by immersion in a corrosive solution of NaCl at 0.05 mol / L in water which are improved.
  • Such properties of physical resistance to mechanical attack are evaluated in particular by techniques known in themselves to those skilled in the art, in particular by nanoindentation for the evaluation of Young's modulus of elasticity and hardness (for example, nano-hardness of Vickers) or by progressive scratching ("nano-scratch”) for the evaluation of the adhesion and the resistance to delamination of the anticorrosion coating on the surface of the solid metal substrate.
  • the cerium cation is a single cerium cation and the concentration of the single cerium cation in the treatment solution is between 0.005 mol / L and 0.015 mol / L, especially between 0.005 mol / L and 0.01 mol. / L, preferably of the order of 0.01 mol / l.
  • the cerium cation is a composition comprising a plurality of distinct cerium cations and the cumulative concentration of the plurality of distinct cerium cations in the treatment solution is itself between 0.005 mol / L and 0.015 mol / L, in particular between 0.005 mol / L and 0.01 mol / L, preferably of the order of 0.01 mol / L.
  • a concentration of cerium cation in the treatment solution of between 0.005 mol / l and 0.015 mol / l according to the invention gives the anticorrosion coating of a solid metal substrate a resistance towards corrosion which is optimal after deposition and before immersion in a corrosive solution.
  • a concentration of cerium cation in the treatment solution of greater than 0.015 mol / L leads to a significant degradation of the barrier effect of the protective layer and a reduced resistance to corrosion before immersion in a corrosive solution.
  • the surface resistance in a corrosive medium of such a protective layer of 6.3 ⁇ m thick, obtained by an anticorrosion treatment of a solid metal substrate with a treatment solution containing 0.05 mol / l of cerium cation, and immediately after immersion of said metal substrate in the corrosive medium is of the order of 2.8 ⁇ 10 6 ⁇ .cm 2 .
  • the surface resistance in corrosive medium of such a protective layer of 6.3 ⁇ m thick, obtained by an anticorrosion treatment of a solid metal substrate with a treatment solution containing 0.1 mol / l of cerium cation, and immediately after immersion of said metal substrate in the corrosive medium is of the order of 2.0 ⁇ 10 5 ⁇ .cm 2 as measured by electrochemical impedance spectroscopy (EIS).
  • the inventors have observed that such a concentration of cerium cations of between 0.005 mole / L and 0.015 mole / L in the treatment solution is adapted to at least preserve the mechanical properties of the hybrid matrix obtained from the solution. process for imparting to the treatment solution rheological and surface adherence properties of the solid metal substrate which are improved over a treatment solution not having such a concentration, while imparting to said hybrid matrix passive protection of the solid metal substrate by barrier effect.
  • each alkoxysilane is selected from the group consisting of tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), tetraacetoxysilane (TAOS) and tetra-2-hydroxyethoxysilane (THEOS). .
  • TEOS tetraethoxysilane
  • TMOS tetramethoxysilane
  • TAOS tetraacetoxysilane
  • TEEOS tetra-2-hydroxyethoxysilane
  • the R 3 group of each alkoxysilane is selected from the group consisting of methacrylates, acrylates, vinyls, epoxyalkyls and epoxyalkoxyalkyls in which the group (s) ( s) alkyl has from 1 to 10 carbon atoms and is (are) selected from linear alkyl groups, branched alkyl groups and cyclic alkyl groups.
  • the R 3 group of each alkoxysilane is selected from the group consisting of 3,4-epoxycyclohexylethyl and glycidoxypropyl.
  • each alkoxysilane is selected from the group consisting of glycidoxypropyltrimethoxysilane (GPTMS), glycidoxypropylmethyldimethoxysilane (MDMS), glycidoxypropylmethyldiethoxysilane (MDES) of glycidoxypropyltriethoxysilane (GPTES), methyltriethoxysilane (MTES), dimethyldiethoxysilane (DMDES), methacryloxypropyltrimethoxysilane (MAP).
  • GTMS glycidoxypropyltrimethoxysilane
  • MDMS glycidoxypropylmethyldimethoxysilane
  • MDES glycidoxypropylmethyldiethoxysilane
  • GPTES glycidoxypropyltriethoxysilane
  • MTES methyltriethoxysilane
  • DMDES dimethyldiethoxysilane
  • MAP methacryloxypropyltrime
  • ECHETES 3- (trimethoxysilyl) propylamine
  • ECHETES 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane
  • ECHETMS 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane
  • EHTES 5,6 epoxyhexyltriethoxysilane
  • an organic / inorganic hybrid matrix is formed by hydrolyzing the condensation of each alkoxysilane.
  • the treatment solution comprises a single alkoxysilane.
  • the treatment solution comprises at least one metal alkoxide.
  • each reactive species homogeneously distributed in the treatment solution and able to polymerize and form an organic / inorganic hybrid matrix are formed by hydrolysis of each alkoxysilane and each metal alkoxide.
  • An organic / inorganic hybrid matrix is thus formed by condensation hydrolysis of each alkoxysilane and each metal alkoxide.
  • each metal alkoxide is selected from the group consisting of aluminum alkoxides, especially aluminum tri ( s- butoxide), aluminum tri ( n- butoxide), aluminum tri (ethoxide), aluminum, aluminum tri (ethoxyethoxyethoxide) and aluminum tri ( iso- propoxide), titanium alkoxides -including titanium tetra ( n- butoxide), titanium tetra ( iso- butoxide), tetra ( iso- propoxide) of titanium, titanium tetra (methoxide) and titanium tetra (ethoxide), vanadium alkoxides, especially vanadium tri ( iso- butoxide) oxide and vanadium tri ( iso- propoxide) oxide and alkoxides; zirconium-especially tetra (ethoxide) zirconium, tetra (iso-propoxide) zirconium, tetra (n -propoxyde) zirconium, te
  • the treatment solution comprises a single metal alkoxide.
  • An inorganic hybrid matrix is thus formed by condensation hydrolysis of each alkoxysilane and the single metal alkoxide.
  • the treatment solution comprises a single metal alkoxide and a single alkoxysilane.
  • An inorganic hybrid matrix is thus formed by condensation hydrolysis of the single alkoxysilane and the single metal alkoxide.
  • the treatment solution comprises, as a single metal alkoxide, a single aluminum alkoxide.
  • a treatment solution comprising a metal alkoxide, especially a single aluminum alkoxide and a single alkoxysilane, said treatment solution being of great simplicity in its composition and still suitable for providing a high performance anticorrosive coating.
  • the single aluminum alkoxide is selected from the group consisting of aluminum tri ( s- butoxide), aluminum tri ( n- butoxide), aluminum tri (ethoxide), tri (ethoxyethoxyethoxide) ) aluminum and tri ( iso propoxide) aluminum.
  • the molar ratio of the alkoxysilanes with respect to the metal alkoxides in the treatment solution is between 99/1 and 50/50.
  • the molar ratio of all the alkoxysilanes relative to the total of metal alkoxides in the treatment solution is between 99/1 and 50/50.
  • the molar ratio of alkoxysilanes and metal alkoxides-in particular aluminum alkoxide-in the treatment solution is between 85/15 and 6/4 in particular between 8/2 and 64/36.
  • the molar ratio of all the alkoxysilanes relative to the total of metal alkoxides in the treatment solution is between 8/2 and 6/4.
  • the solid metal substrate is formed of a material chosen from the group consisting of oxidizable materials-in particular aluminum (for example alloy 2024T3), titanium (for example alloy TA6V) , magnesium (for example, the AZ30 alloy) and their alloys.
  • aluminum for example alloy 2024T3
  • titanium for example alloy TA6V
  • magnesium for example, the AZ30 alloy
  • the treatment solution is applied by soaking / removal of the solid metal substrate in said treatment solution.
  • the solid metal substrate is removed from the treatment solution with a predetermined speed of between 5 cm / min and 10 cm / min.
  • the atmospheric spray treatment solution is applied to the surface of the solid metal substrate.
  • the inventors have observed that it is possible to control the thickness of the hybrid matrix by the rate of removal of the solid metal substrate from the treatment solution.
  • a known viscosity treatment solution to vary the thickness of the hybrid anti-corrosion matrix by a value of 1 ⁇ m for a withdrawal speed of 1 cm / min, up to a value of 14. ⁇ m for a withdrawal speed of 20 cm / min.
  • a withdrawal rate of 7 cm / min makes it possible to obtain a hybrid matrix with a thickness of 5 ⁇ m.
  • the thickness of the hybrid matrix is measured by methods known in themselves to those skilled in the art, in particular by interferometric profilometry or by measurement of induced eddy currents.
  • the treatment solution further comprises a plasticizer selected from the group consisting of PEG.
  • the liquid treatment solution comprises a dye.
  • a dye is selected from the group consisting of rhodamine B (CAS 81-88-9), malachite green ("brilliant green", CAS 633-03-4) and xylene cyanole (CAS 2850-17-1). ).
  • rhodamine B is used at a concentration in the liquid treatment solution of between 5.10 -4 mol / l and 10 -3 mol / l, the malachite green at a concentration in the liquid treatment solution of between 5.10 -4. mol / L to 10 -3 mol / L and xylene cyanole at a concentration in the liquid treatment solution between 5.10 -4 mol / L to 10 -3 mol / L.
  • the treatment solution comprises a nanoparticle feedstock formed of a colloidal dispersion of boehmite in the treatment solution, that is to say solid nanoparticles of boehmite of general formula [-AlO (OH) -] forming a colloidal dispersion of boehmite nanoparticles in the treatment solution.
  • an alcoholic solution is added alkoxysilane (s) and the (the) alkoxide (s) metal (s) and an amount of water or, if appropriate, an amount of an aqueous solution containing at least one lanthanide cation and / or nanoparticles of colloidal boehmite so as to substantially retain the rheological and thixotropic properties of the treatment solution.
  • a treatment solution comprising boehmite nanoparticles of general formula AlO (OH) and having a surface distribution of lanthanide cations -including cerium- and / or vanadate cations.
  • boehmite nanoparticles called physisorbed boehmite nanoparticles, are obtained by a process known in itself to those skilled in the art and in particular adapted from a process described by Yoldas ( Yoldas BE et al., (1975), J. Mater. Sci., 10, 1856 ).
  • the inventors have found an improvement in the corrosion resistance of a solid metal substrate treated with a treatment solution subjected to immersion in a corrosive bath of NaCl at 0, 05 mole / L.
  • Such doped boehmite nanoparticles are obtained by a process in which a solution of at least one aluminum precursor - notably Al (OC 4 H 9 ) 3 - in water and a solution of a cation of a doping element selected from the group consisting of a nitrate, a sulfate, an acetate and a chloride of the doping element.
  • a solution of at least one aluminum precursor - notably Al (OC 4 H 9 ) 3 - in water and a solution of a cation of a doping element selected from the group consisting of a nitrate, a sulfate, an acetate and a chloride of the doping element.
  • the inventors have found an improvement in the corrosion resistance of a solid metal substrate treated with a treatment solution subjected to immersion in a corrosive bath of NaCl at 0, 05 mole / L.
  • the physisorbed boehmite nanoparticles and the doped boehmite nanoparticles have a larger dimension and two smaller dimensions, perpendicular to each other and perpendicular to said larger dimension, said larger dimension is less than 200 nm. -In particular less than 100 nm, particularly less than 50 nm, preferably between 5 nm and 20 nm-, and the two smaller dimensions are less than 10 nm, preferably of the order of 3 nm.
  • the treatment solution comprises a charge of hollow boehmite nanoparticles.
  • a heat treatment of the metal substrate adapted to allow the formation of the hybrid matrix and the evaporation of the solvents is carried out.
  • said oxidizable surface of the solid metal substrate is immersed in a so-called conversion solution solution, a liquid formed of at least one corrosion inhibitor in water said corrosion inhibitor being selected from the group consisting of lanthanide cations and said oxidizable surface of the solid metal substrate is held in contact with the conversion solution for a period of time suitable to form a conversion layer formed from said bound lanthanide by at least one covalent bond to the oxidizable surface and extending at the surface of the solid metal substrate.
  • a conversion layer is first formed on the oxidizable surface of a solid metal substrate by contacting said oxidizable surface with the conversion solution.
  • a treatment with such a conversion solution constitutes an anticorrosion treatment in that it allows the formation of a surface conversion layer of the solid metal substrate, instead of a metal oxide layer of the solid metal substrate.
  • said conversion layer exhibiting a resistance to corrosion - in particular measured by electrochemical impedance spectroscopy (EIS) - which is increased with respect to the corrosion resistance of the coating layer. oxide formed naturally on the surface of the solid metal substrate.
  • an anticorrosion treatment according to the invention in which a layer of surface conversion of a solid metal substrate, then a treatment solution comprising at least one alkoxysilane, a cerium cation at a concentration of between 0.005 mol / L and 0.015 mol / L, and, where appropriate, at least one metal alkoxide, makes it possible to increase the resistance to corrosion of the oxidizable surface of a solid metal substrate, even after immersion of the oxidizable surface of the solid metal substrate for a predetermined period of time -particularly a duration greater than 1 hour- in a bath of corrosion, especially an aqueous bath of NaCl 0.05 mol / L.
  • Such a conversion layer is characterized, according to a representation, called "Nyquist" representation, of the electrochemical impedance diagram by a value Z '( ⁇ ) of surface resistance ( ⁇ .cm 2 ) increased compared with the value Z' (co) the surface resistance of a solid metal oxide layer naturally formed on the surface of a solid metal substrate.
  • the impedance measurements Z (co) are carried out in potentiostatic mode around the free potential, with a sinusoidal disturbance.
  • the amplitude of sinusoidal disturbance is set at 10 mV in order to satisfy the linearity conditions.
  • the frequencies scanned during impedance measurements are between 65 kHz and 10 mHz with 10 points per decade.
  • EDS Energy Dispersive Spectroscopy
  • the conversion layer extending at the surface of the solid metal substrate has an average thickness of between 1 nm and 200 nm.
  • the inventors have observed that increasing the immersion time of a solid metal substrate in a conversion solution according to the invention makes it possible to increase the value of the surface area resistance which goes beyond the limit value of the surface resistance of the layer of aluminum oxide formed naturally on the surface of a piece of alloy of aluminum.
  • the treatment of the oxidizable surface of the solid metal substrate by the conversion solution allows the formation of an active protection conversion and healing layer on the surface of the solid metal substrate by formation of a plurality of covalent bonds occurring between the lanthanide element (Ln) corrosion inhibitor and a metal element (M) of the solid metal substrate.
  • Ln lanthanide element
  • M metal element
  • the inventors have shown by chemical analysis of the binding energies - in particular by X-ray photoelectron spectrometry (XPS) - that this covalent bond is of the MO-Ln-O- type in which M represents a metallic element of the solid metal substrate, O is an oxygen atom and Ln represents the corrosion inhibiting element chosen from lanthanides.
  • a treatment solution formed of an organic / inorganic hybrid soil of at least one alkoxysilane is applied to the oxidizable surface of the solid metal substrate, and optionally to the surface of the conversion layer.
  • the inventors have observed that immersing a solid metal substrate in a conversion solution allows not only the formation of such a conversion layer and the active protection of the solid metal substrate against corrosion, but also allows an improvement of the adhesion of a hybrid soil surface of the solid metal substrate and an improvement of passive protection properties of said solid metal substrate against corrosion.
  • each corrosion inhibitor of the conversion solution is selected from the group consisting of lanthanum (La) cations, cerium (Ce) cations, praseodymium (Pr) cations, neodymium cations. (Nd), samarium (Sm) cations, europium (Eu) cations, gadolinium (Gd) cations, terbium (Tb) cations, dysprosium (Dy) cations, holmium cations (Ho), erbium cations (Er), thulium cations (Tm), ytterbium cations (Yb) and lutetium cations (Lu).
  • La lanthanum
  • Ce cerium
  • Pr praseodymium
  • Nd samarium
  • Eu europium
  • Gd gadolinium
  • Tb terbium
  • Dy dysprosium
  • Ho holmium cations
  • Er er
  • each corrosion inhibitor of the conversion solution is chosen from the group formed by lanthanide chlorides, lanthanide nitrates, lanthanide acetates and lanthanide sulfates.
  • each corrosion inhibitor of the conversion solution in the group consisting of lanthanum chloride (LaCl 3), cerium chloride (CeCl 3), yttrium chloride (YCl 3), cerium sulfate ( Ce 2 (SO 4 ) 3 ), cerium acetate (Ce (CH 3 COO) 3 ), praseodymium chloride (PrCl 3 ), neodymium chloride (NdCl 3 )
  • each corrosion inhibitor of the conversion solution is a cerium cation-notably cerium nitrate (Ce (NO 3 ) 3 ), cerium acetate (Ce (CH 3 COO) 3 ) , cerium sulphate (Ce 2 (SO 4 ) 3 ) and cerium chloride (CeCl 3 ) - in which the cerium element is of valence III (Ce III ).
  • the cerium cation (Ce) of the treatment solution is chosen from the group formed by cerium chlorides and cerium nitrates.
  • the corrosion inhibitor of the conversion solution is cerium nitrate Ce (NO 3 ) 3 .
  • the conversion layer consists of mixed oxides of cerium and the constituent metal of the oxidizable surface of the solid metal substrate.
  • the chemical analysis by energy dispersive spectroscopy (“EDS”) shows L ⁇ and M ⁇ lines characteristic of cerium bound by covalent liaiasons on the surface of the solid metal substrate.
  • an anticorrosion treatment method makes it possible to form an anticorrosion coating formed of a conversion layer comprising at least one corrosion inhibitor and adapted to allow self-healing of the solid metal substrate, said conversion layer being it is protected by the cerium-rich hybrid matrix with an optimal barrier effect.
  • the conversion solution has a concentration of corrosion inhibitor - in particular cerium (Ce) - of between 0.001 mol / l and 0.5 mol / l, in particular between 0.05 mol / l and 0, 3 mol / L, in particular of the order of 0.1 mol / L.
  • Ce cerium
  • the conversion solution has a concentration of corrosion inhibitor - in particular cerium (Ce) - of between 0.01 mole / L and 0.5 mole / L, preferably between 0.1 mole / L and 0.5 mol / L.
  • Ce cerium
  • the oxidizable surface of the solid metal substrate is maintained in contact with the conversion solution for a predetermined period of between 1 s and 30 min, in particular between 1 s and 300 s, preferably between 1 s and 15 s, in particular between 1 s and 10 s, more preferably between 1 s and 3 s.
  • the solid metal substrate is dried at a predetermined temperature of less than 100 ° C., in particular of the order of 50 ° C. in order to form on the surface of the solid metal substrate, a layer, referred to as the conversion layer, of the corrosion inhibitor element Ln (lanthanide) bonded to a metal element M of the solid metal substrate by a bond of the MO-Ln type. O-.
  • the conversion solution has a pH substantially of the order of 4.
  • the pH of the conversion solution is adjusted by addition of a mineral acid - in particular nitric acid - to the conversion solution.
  • the inventors have observed that a method of anticorrosion treatment of a solid metal substrate in two stages according to the invention not only allows an active protection, in particular by healing, of the solid metal substrate with respect to corrosion but also provides passive protection against said corrosion.
  • the liquid aqueous-alcoholic composition is formed of water and at least one alcohol -notamment selected from the group consisting of ethanol, propanol-1 and propanol-2-.
  • doped and / or physisorbed boehmite nanoparticles have a larger dimension and two smaller dimensions, perpendicular to each other and perpendicular to said larger one.
  • dimension, said largest dimension is less than 200 nm, especially less than 100 nm, particularly less than 50 nm, preferably between 5 nm and 20 nm, and the two smaller dimensions are less than 10 nm, preferably less than the order of 3 nm.
  • the treatment solution comprises a charge of hollow boehmite nanoparticles.
  • the invention also relates to an anticorrosion coating that can be obtained by a process according to the invention.
  • the invention also extends to an anticorrosion coating of a solid metal substrate formed of a hybrid matrix extending at the surface of the solid metal substrate and obtained by hydrolysis / condensation of at least one alkoxysilane; said hybrid matrix having a molar ratio (Si / Ce) of silicon element of the alkoxysilane (s) with respect to at least one cerium (Ce) cation of between 50 and 500, in particular between 80 and 250.
  • This Ce / Si ratio is determined by methods known in themselves to those skilled in the art, in particular by RBS (Rutherford Backscattering Spectrometry) analysis of the elastic diffusion of the ions of an incident ion beam adapted to be able to measure the amount of a heavy element in a light hybrid matrix.
  • RBS Rutherford Backscattering Spectrometry
  • the anticorrosion coating has a thickness of between 1 micron and 15 microns.
  • the conversion layer of the anticorrosion coating has a thickness of between 1 nm and 200 nm.
  • the invention also extends to a metal surface coated with an anticorrosion coating obtained by a method according to the invention.
  • the invention also relates to a process characterized in combination by all or some of the characteristics mentioned above or below.
  • An anticorrosion coating 1 according to the invention represented in figure 1 is supported on a metal substrate 2 formed of metallic elements M.
  • Such an anticorrosive coating is formed of an optional conversion layer 3 in which corrosion inhibiting elements Ln are linked by MO-Ln- covalent bonds to metallic elements M of the metal substrate 2.
  • conversion layer corrosion inhibitor elements Ln form covalent bonds with Si elements and, where appropriate, metal elements M 'chosen from the group consisting of aluminum (Al), vanadium (V ) titanium (Ti) and zirconium (Zr) and the cerium element (Ce) of the hybrid matrix 4 extending on the surface of the conversion layer 3.
  • the figure 2 represents a scanning electron microscopy (SEM) section of an aluminum substrate 2 treated with an alternative of a method according to the invention and comprising a conversion layer (optional) 3 extending at the interface between the aluminum substrate 2 and the hybrid matrix 4.
  • SEM scanning electron microscopy
  • a preparative surface treatment of a piece of rolled 2024 T3 aluminum alloy is first carried out.
  • Such a preparative treatment aims to eliminate from the surface of the solid metal substrate any trace of oxidation of the alloy or of staining which may hinder the homogeneous application of the conversion solution and the treatment solution on the surface of the substrate during its deposition ("dip-coating", "spray") and the anchoring of the hybrid anti-corrosion matrix obtained at the surface of the substrate.
  • the preparative treatment comprises a first step of degreasing the surface of the solid metal substrate during which the surface of said substrate is placed in contact with a degreasing solvent.
  • This degreasing step is carried out by methods known in themselves to those skilled in the art, in particular by soaking the surface of the substrate in the degreasing solvent or by spraying said surface with the degreasing solvent.
  • the degreasing solvent may be stabilized pure methylene chloride (marketed under the trademark Methoklone) or pure acetone.
  • this degreasing step is carried out at a temperature below 42 ° C. and for a duration of between 5 seconds and 3 minutes. It is possible to subject the solid metal substrate to ultrasonic treatment during this first degreasing step.
  • the preparative treatment of the solid metal substrate comprises a second successive step of degreasing the surface of said substrate in which the surface of the substrate is placed in contact with an alkaline preparation, in particular marketed under the trademark TURCO 4215 (HENKEL, Boulogne-Billancourt, France). ).
  • This alkaline degreasing step is carried out by methods known in themselves to those skilled in the art, in particular by soaking the surface of the substrate in the alkaline preparation or by spraying said surface with said preparation for a period of between 10 minutes and 30 min.
  • this alkaline degreasing step is carried out at a temperature of between 50 ° C. and 70 ° C. It is possible to subject the substrate to an ultrasonic treatment during this second degreasing step with an alkaline solution.
  • the preparative treatment according to the invention comprises a third successive step of pickling the surface of the substrate in which the surface of the substrate is placed in contact with an alkaline preparation, in particular an aqueous solution of sodium hydroxide at a concentration of between 30.degree. g / L at 70 g / L.
  • This alkaline pickling step is carried out by methods known in themselves to those skilled in the art, in particular by soaking the surface of the substrate in the concentrated alkaline preparation or by spraying said surface with said concentrated alkaline preparation for a period of time between 10 sec and 3 min.
  • this alkaline pickling step is carried out at a temperature of between 20 ° C. and 50 ° C. It is possible to subject the solid metal substrate to ultrasonic treatment during this second etching step with a concentrated alkaline solution.
  • the preparative treatment according to the invention comprises a fourth successive stage of dissolution of the oxide layer extending over the surface of the solid metal substrate in which the surface of said substrate is placed in contact with an acid preparation, for example TURCO LIQUID Smut-Go NC (HENKEL, Boulogne-Billancourt, France) or ARDROX 295 GD (Chemetal GmbH, Frankfurt, Germany) .
  • an acid preparation for example TURCO LIQUID Smut-Go NC (HENKEL, Boulogne-Billancourt, France) or ARDROX 295 GD (Chemetal GmbH, Frankfurt, Germany) .
  • This dissolution step is carried out for a period of between 1 min and 10 min at a temperature of between 10 ° C. and 50 ° C. with an aqueous solution comprising between 15% (v / v) and 25% (v / v) of TURCO LIQUID Smut-Go NC.
  • this dissolution step is carried out for a period of between 1 min and 10 min at a temperature of between 10 ° C. and 30 ° C. with an aqueous solution comprising between 15% (v / v) and 30% (v / v).
  • aqueous solution comprising between 15% (v / v) and 30% (v / v).
  • the surface of the solid metal substrate is adapted to be treated according to an anticorrosion treatment according to the invention.
  • a step of forming a surface conversion layer of the solid metal substrate is carried out.
  • a piece of aluminum (Al 2024-T3) is immersed by "dip-coating" in an aqueous conversion solution containing a concentration of between 0.001 mol / l and 0.5 mol / l of Ce (NO 3 ) 3 , the pH is adjusted to a value of 4 by adding nitric acid. After immersion and shrinkage, the aluminum piece is dried for 10 minutes at 50 ° C. At the end of this treatment with the conversion solution, no weight gain of said aluminum piece is measured.
  • An aqueous solution of cerium (III) (Ce (NO 3 ) 3 ) at a concentration of between 0.02 mol / l and 0.5 mol / l is also prepared, and a volume of this aqueous solution of cerium is added to the solution.
  • precursor ASB / GPTMS
  • the epoxy sol obtained is stirred for a period of time necessary for a thermal decline to ambient temperature.
  • the final concentration of cerium in the epoxy sol is 0.01 mol / L.
  • TEOS tetraethoxysilane
  • MAP methacryloxypropyltrimethoxysilane
  • the pH of the sol obtained is 4.5 and its viscosity is 3 mPa.s.
  • Such a colloidal dispersion of surface-functionalized boehmite nanoparticles is produced in two steps, described below, in which a colloidal solution of boehmite nanoparticles is first formed, and then said boehmite nanoparticles are functionalized with an inhibitor of corrosion.
  • Condensation hydrolysis of tri- sec butoxide (ASB, Al (OH) x (OC 4 H 9 ) 3-x ) of aluminum is carried out according to the method described by Yoldas BE ( J. Mater. Sci., (1975), 10, 1856 ), in which an amount of water preheated to a temperature above 80 ° C is added to tri- sec- butoxide of aluminum. The resulting solution is left stirring for 15 minutes.
  • such a solution of aluminum tri ( s- butoxide) at a concentration of 0.475 mol / l ( ⁇ 117 g / l) in water at a temperature of 80 ° C. for one duration of 15 min. Is then carried out step, said step of peptization, at which is added to the dry tri- butoxide hydrolysis solution a volume of between 1.4 ml and 2.8 ml of a nitric acid solution at 68 %.
  • the mixture is placed at 85 ° C. in an oil bath for a period of 24 hours.
  • a colloidal dispersion of oxyhydroxide is obtained aluminum (boehmite) in the water.
  • the concentration of nitric acid in the colloidal dispersion is between 0.033 mole / L and 0.066 mole / L.
  • Other inorganic or organic acids may be used during this peptization step, in particular hydrochloric acid and acetic acid.
  • a transparent and stable colloidal substrate having, by X-ray diffraction, the characteristic lines of boehmite as described in JCPDS sheet 21-1307 is obtained.
  • a nonionic surfactant especially a non-surfactant
  • ionic material chosen from Pluronic® P-123, Pluronic® F 127 (BASF, Mount Olive, New Jersey, USA), Brij 58 and Brij 52 in a final mass proportion of between 1% and 5%.
  • An amount of a corrosion inhibitor in particular cerium (III) nitrate (Ce (NO 3 ) 3 ) or sodium vanadate, is then added to a final concentration of between 0.001 mol / l and 0.5 mol / ml. L.
  • This preparation is stirred at room temperature for a period of 6 hours.
  • Such a preparation is present in infrared spectroscopy by using the Diffuse Reflectance Infra-red Fourier Transform (DRIFT) technique of the 1460 cm -1 and 1345 cm -1 vibration bands characteristic of the coordination of cerium with nitrate ions.
  • Diffuse Reflectance Infra-red Fourier Transform Diffuse Reflectance Infra-red Fourier Transform
  • Such a colloidal dispersion of boehmite nanoparticles doped in two steps described below is carried out in which (C1) is carried out the hydrolysis / condensation of a precursor - in particular an aluminum alkoxide and a corrosion inhibitor.
  • a step (C2) called a step of peptization, acid treatment in order to form doped boehmite nanoparticles.
  • the hydrolysis / condensation of a mixture of aluminum precursor - in particular an aluminum alkoxide, in particular aluminum tri ( s- butoxide) (ASB) - and a corrosion inhibitor - is carried out. in particular cerium (III) nitrate (Ce (NO 3 ) 3 ) - by adding to this mixture a minimum of water heated to the temperature of 85 ° C.
  • ASB aluminum tri
  • Ce (NO 3 ) 3 cerium
  • This hydrolysis / condensation mixture is placed under stirring for 15 minutes.
  • the final concentration of ASB in the hydrolysis / condensation mixture is 0.475 mol / L and the final concentration of corrosion inhibitor in the hydrolysis / condensation mixture is between 0.005 mol / L and 0.015 mol / L.
  • the concentration of nitric acid in the acidified mixture is between 0.033 mol / L and 0.066 mol / L.
  • a transparent and stable colloidal sol having, by X-ray diffraction, the characteristic lines of boehmite as described in JCPDS sheet 21-1307 is obtained.
  • Such hollow aluminum oxyhydroxide nanoparticles containing the corrosion inhibitor are produced by formation of an inverse microemulsion ( Daniel H., et al (2007), Nano Lett., 7; 11, 3489-3492 ) and simultaneous encapsulation of the corrosion inhibitor.
  • An apolar phase is prepared by mixing an alcohol, in particular hexanol, an alkane, especially dodecane, and a surfactant, especially hexadecyltrimethylammonium bromide (CTAB).
  • CTAB hexadecyltrimethylammonium bromide
  • a polar phase comprising water, an alcohol - in particular methanol - and a corrosion inhibitor - in particular cerium nitrate -.
  • the polar phase and the apolar phase are mixed and this mixture is stirred for 30 minutes to form a reverse microemulsion of water in the apolar phase.
  • a solution of an aluminum alkoxide - especially aluminum tri ( t- butoxide) (ASB) in a volume of the alkane - especially dodecane - is prepared.
  • the aluminum alkoxide solution is introduced with stirring into the inverse microemulsion.
  • the mixture is allowed to stand for 12 hours.
  • a pellet containing hollow nanoparticles of aluminum oxyhydroxide is centrifuged off. After washing this pellet with diethylene glycol, a hollow aluminum oxyhydroxide nanoparticle powder containing the corrosion inhibitor is obtained.
  • Such a colloidal anticorrosive treatment dispersion is prepared by mixing an amount of a treatment solution (hybrid sol) as prepared in (A) with an amount of colloidal dispersion of physisorbed boehmite nanoparticles as prepared in B) and / or an amount of a colloidal dispersion of doped boehmite nanoparticles as prepared in (C) and / or an amount of a dispersion of hollow boehmite nanoparticles.
  • the concentration of aluminum and silicon in the colloidal anti-corrosion treatment dispersion is between 1.66 mol / l and 2 mol / l.
  • the aluminum concentration provided by the colloidal dispersion of surface-functionalized boehmite nanoparticles in the hybrid soil is between 0.1 mol / l and 0.13 mol / l.
  • the aluminum concentration provided by the colloidal dispersion of doped boehmite nanoparticles in hybrid soil is between 0.1 mol / l and 0.13 mol / l.
  • the hybrid soil thus obtained is allowed to stand at ambient temperature for a period of 24 hours.
  • an alcoholic solution containing at least one alkoxysilane and at least one aluminum alkoxide is prepared and then an amount of the dispersion is added to the alcoholic solution.
  • colloidal of physisorbed boehmite nanoparticles and / or doped boehmite nanoparticles and / or hollow boehmite nanoparticles is prepared and then an amount of the dispersion is added to the alcoholic solution.
  • the viscosity of the treatment solution (dispersion) which decreases with the addition of the colloidal dispersion of boehmite is controlled in this way.
  • a step is performed for depositing the colloidal anti-corrosion treatment dispersion on a surface of a solid metal substrate, in particular a part of a rolled aluminum alloy 2024 T3 having previously undergone degreasing and pickling.
  • a part of the solvent of the composite hybrid soil evaporates and simultaneously the hydrolysis / condensation of (the) alkoxysilane (s) and (s) alkoxide (s) metal (s) allows the formation of a composite hybrid anti-corrosion matrix on the surface of the solid metal substrate.
  • cerium as a corrosion inhibitor, especially free cerium (Ce III ), in the treatment solution allows the formation during the deposition of said solution of a chemically stable conversion layer in a corrosive medium.
  • a conversion layer is in particular formed from the hydroxyl groups of an element M constituting the solid metal substrate and forming an MO-Ce- bond with cerium.
  • the presence of physisorbed boehmite nanoparticles and doped boehmite nanoparticles in the treatment solution is adapted to allow the formation of corrosion inhibitor reservoirs in the composite hybrid matrix constituting the anticorrosion coating, said reservoirs being adapted to allow controlled release. in time of the corrosion inhibitor.
  • the application of the surface treatment solution of the solid metal substrate is carried out by any means known in itself to those skilled in the art, in particular by soaking / shrinking ("dip coating”), by spraying (“spray-coating”), or by brush, pad or brush application for localized uses as a coating repair of the surface of the solid metal substrate.
  • dip coating soaking / shrinking
  • spraying spraying
  • brush, pad or brush application for localized uses as a coating repair of the surface of the solid metal substrate.
  • the shrinkage rate makes it possible to control the thickness of the deposition of the treatment solution for a viscosity of the given treatment solution.
  • the withdrawal speed varies between 2 and 53 cm / min.
  • the extended residence time may vary between 1 and 300 seconds.
  • the thickness of the deposits is controlled by the viscosity of the treatment solution, the sputtering parameters, including the pressure, the flow rate, the geometric characteristics of the spray nozzles, and the speed of movement. nozzles facing the surface of the solid metal substrate and the number of passage of the nozzles in front of the surface of the solid metal substrate.
  • the application of the treatment solution can be carried out manually or be robotized according to conventional techniques.
  • the thickness of the deposit is controlled by the viscosity of the treatment solution and by the number of successive applications on the surface of the solid metal substrate.
  • the treatment solution applied to the surface of the solid metal substrate is heat-treated so as to evaporatively remove the residual solvent (s) from the treatment solution and allow it to polymerize into a hybrid matrix. composite.
  • a heat treatment comprises two successive steps in which the solid metal substrate coated with the treatment solution is first subjected to a first heating step at a temperature between 50 ° C and 70 ° C for a period of time between 2 h and 24 h, said first heating step being adapted to allow removal of aqueous and / or organic solvents, then to a second heating step at a temperature between 110 ° C and 180 ° C for a period of time between 3 h and 16 h, said second heating step being adapted to perfect the polymerization of the treatment solution and to improve the mechanical properties of the composite hybrid matrix.
  • the figure 3 represents the variation of the surface resistance of a solid metal substrate treated by a method according to the invention as a function of the immersion time of this solid metal substrate in a corrosion bath (NaCl 0.05 mol / L in the water).
  • the curve ( ⁇ ) represents the variation of the surface resistance of a solid metal substrate treated according to a process according to the invention consisting in the successive application of a conversion solution rich in cerium (0.1 mol / L) then a treatment solution comprising cerium (0.01 mol / L). It is observed that the surface resistance of the treated solid metal substrate ( ⁇ ) decreases more slowly than the surface resistance of a solid metal substrate ( ⁇ ) treated with the same treatment solution (0.01 mol / L of Ce) but free of conversion layer.
  • the surface resistance of the untreated substrate ( ⁇ ) reaches a value of the order of 2.12 10 6 ⁇ .cm 2 , while the resistance surface area (•) treated remains of the order of 4.05 10 6 ⁇ .cm 2 .
  • the surface resistance of the untreated substrate ( ⁇ ) reaches a limit value of the order of 1.1 ⁇ 10 6 ⁇ .cm 2 , whereas the surface resistance of the substrate ( ) treated remains of the order of 2.75 10 6 ⁇ .cm 2 .
  • the inventors have also observed, in a completely surprising and unexpected manner, that the anticorrosion treatment of a solid metal substrate according to the invention with a treatment solution comprising a cerium concentration of between 0.005 mol / l and 0.015 mol / l allows not only to obtain a surface resistance of the anticorrosion coating, measured by electrochemical impedance spectroscopy ( figure 4 ), which is optimal for an immersion time of the solid metal substrate in a corrosion bath of 1 day ( ⁇ ), 7 days ( ⁇ ) and 14 days ( ⁇ ) in an aqueous solution of NaCl 0.05 mol / L , but that such a treatment also makes it possible to obtain a nano-hardness ( figure 5 ), a Young's module ( figure 6 ) and resistance to delamination ( ⁇ , figure 7 ), resistance to cracking ( ⁇ , figure 7 ) and a limit value of resistance to plastic deformation ( ⁇ , figure 7 ) also maximum.
  • a treatment solution comprising a cerium concentration of between 0.005 mol / l
  • Electrochemical impedance spectroscopy is used to analyze the corrosion resistance of a solid metal substrate Al 2024-T3 treated or not with a conversion solution and then exposed to a step of corrosion by immersion in an aqueous solution of NaCl 0.05 mole. / L.
  • the results are presented in figure 8 according to the representation of Nyquist.
  • a corrosion solution NaCl 0.05 mol / L
  • the treatment of a piece of raw aluminum 2024-T3 (that is to say, not treated with a conversion solution) by immersion in a corrosion solution gives the latter a surface resistance Z ' of the order of 5.10 3 ⁇ .cm 2 ( ⁇ , figure 8 ).
  • the residual surface resistance Z 'of such a piece of aluminum after 1 hour of immersion in the corrosion solution is of the order of 1.1 ⁇ 10 4 ⁇ .cm 2 for a cerium concentration of 0, 01 mole / L in the conversion solution and a conversion treatment duration of 1 s, of the order of 2.10 4 ⁇ .cm 2 for a cerium concentration of 0.05 mol / L in the conversion solution and a conversion treatment duration of 1 s and of the order of 3.3 ⁇ 10 4 ⁇ .cm 2 for a cerium concentration of 0.1 mol / L in the conversion solution and a conversion treatment duration of 1 s.
  • the residual surface resistance Z 'of an aluminum piece after 1 h immersion in the corrosion solution is of the order of 1.1 ⁇ 10 4 ⁇ .cm 2 for a cerium concentration of 0.01 mol / L in the solution of conversion and a conversion treatment duration of 1 s, of the order of 2.10 4 ⁇ .cm 2 for a cerium concentration of 0.01 mol / L in the conversion solution and a conversion treatment duration of 60 s and of the order of 3.8 ⁇ 10 4 ⁇ .cm 2 for a cerium concentration of 0.01 mol / L in the conversion solution and a conversion treatment time of 300 s.
  • the residual surface resistance Z 'of an aluminum piece after 1 hour of immersion in the corrosion solution is of the order of 3.2 ⁇ 10 4 ⁇ .cm 2 for a cerium concentration of 0.1 mol / L in the conversion solution and a conversion treatment time of 1 s, of the order of 4.0 ⁇ 10 4 ⁇ .cm 2 for a cerium concentration of 0.1 mol / L in the conversion solution and a duration of conversion treatment of 60 s and of the order of 9.0.10 4 ⁇ .cm 2 for a cerium concentration of 0.1 mol / L in the conversion solution and a conversion treatment time of 300 s.
  • Prolonged immersion in the corrosion bath leads to a decrease in the surface resistance value which reaches the value of the surface resistance of the aluminum oxide in 10 hours.
  • the surface resistance Z 'of a piece of aluminum treated with a conversion solution containing cerium at a concentration of 0.5 mol / l for a period of 1 s, 60 s and 300 s remains greater than 1.10 4 ⁇ . cm 2 after respectively 40 hours, 70 hours and 90 hours of immersion of the aluminum part in the corrosion bath.

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Claims (12)

  1. Verfahren zur Korrosionsschutzbehandlung, in welchem eine flüssige Lösung, die so genannte Behandlungslösung, hergestellt wird, welche umfasst:
    - mindestens ein Alkoxysilan, und
    - mindestens ein Cerkation (Ce);
    in einer flüssigen hydroalkoholischen Zusammensetzung, anschließend die besagte Behandlungslösung auf eine oxidierbare Oberfläche eines festen Metallsubstrats aufgebracht wird, wobei die besagte Behandlungslösung:
    -- geeignet ist, um auf der Oberfläche des festen Metallsubstrats eine Hybridmatrix bilden zu können durch Hydrolyse/Kondensation von jedem(n) Alkoxysilan (en) in Gegenwart von jedem(n) Cerkation (en) (Ce), und
    -- ein Molverhältnis (Si/Ce) des Elements Silizium des(der) Alkoxysilan(e) im Verhältnis zu dem(den) Cerkation(en) (Ce) von zwischen 50 und 500 aufweist;
    dadurch gekennzeichnet, dass die Behandlungslösung derart hergestellt wird, dass das(die) Cerkation(en) (Ce) eine Konzentration von zwischen 0,005 Mol/L und 0,015 Mol/L in der Behandlungslösung aufweisen.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass jedes Alkoxysilan ausgewählt wird aus der Gruppe, welche gebildet wird von:
    - Tetraalkoxysilanen der folgenden allgemeinen Formel (I);

            Si(O-R1)4     (I),

    in welcher:
    -- Si das Element Silizium ist, 0 das Element Sauerstoff ist;
    -- R1 ausgewählt ist aus der Gruppe, welche gebildet wird von:
    --- einer Kohlenwasserstoffgruppe der Formel [-CnH2n+1], wobei n eine Ganzzahl größer oder gleich 1 ist, und;
    --- der 2-Hydroxyethylgruppe (HO-CH2-CH2-), und;
    --- einer Acylgruppe der allgemeinen Formel -CO-R'1, in welcher R'1 eine Kohlenwasserstoffgruppe der Formel [-CnH2n+1] ist, wobei n eine Ganzzahl größer oder gleich 1 ist, und;
    - Alkoxysilanen der folgenden allgemeinen Formel (II) :

            Si(O-R2)4-a(R3)a     (II) ;

    in welcher:
    -- R2 ausgewählt ist aus der Gruppe, welche gebildet wird von:
    --- einer Kohlenwasserstoffgruppe der Formel [-CnH2n+1], wobei n eine Ganzzahl größer oder gleich 1 ist, und;
    --- der 2-Hydroxyethylgruppe (HO-CH2-CH2-), und;
    --- einer Acylgruppe der allgemeinen Formel -CO-R'1, in welcher R'1 eine Kohlenwasserstoffgruppe der Formel [-CnH2n+1] ist, wobei n eine Ganzzahl größer oder gleich 1 ist, und;
    -- R3 eine organische Gruppe ist, welche über eine Si-C-Verbindung an das Element Silizium (Si) des Alkoxysilans gebunden ist;
    -- a eine natürliche Ganzzahl aus dem Bereich ]0 ; 4[ ist.
  3. Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass die Behandlungslösung mindestens ein Metallalkoholat umfasst.
  4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass jedes Metallalkoholat der folgenden allgemeinen Formel (VII) entspricht:

            M'(O-R9)n"     (VII),

    in welcher:
    - M' ein Metallelement ist, ausgewählt aus der Gruppe, welche gebildet wird von Aluminium (Al), Vanadium (V), Titan (Ti) und Zirkonium (Zr),
    - R9 eine aliphatische Kohlenwasserstoffgruppe der Formel [-CnH2n+1] ist, in welcher n eine Ganzzahl größer oder gleich 1 ist, und;
    - n" eine natürliche Ganzzahl ist, welche die Wertigkeit des Metallelements M' ausdrückt.
  5. Verfahren nach einem der Ansprüche 3 oder 4, dadurch gekennzeichnet, dass jedes Metallalkoholat ein Aluminiumalkoholat der folgenden allgemeinen Formel (III) ist:

            Al(OR4)n     (III),

    in welcher:
    - Al und 0 jeweils die Elemente Aluminium und Sauerstoff sind, und;
    - R4 eine aliphatische Kohlenwasserstoffgruppe ist, welche 1 bis 10 Kohlenstoffatome aufweist;
    - n eine natürliche Ganzzahl ist, welche die Wertigkeit des Elements Aluminium (Al) ausdrückt.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das feste Metallsubstrat aus einem Material gebildet ist, welches ausgewählt ist aus der Gruppe, die von den oxidierbaren Materialien gebildet wird.
  7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass vor Aufbringen der Behandlungslösung die besagte oxidierbare Oberfläche des festen Metallsubstrats in eine flüssige Lösung, die so genannte Umwandlungslösung getaucht wird, welche von mindestens einem Korrosionsinhibitor in Wasser gebildet wird, wobei der besagte Korrosionsinhibitor ausgewählt ist aus der Gruppe, welche von den Lanthanoid-Kationen gebildet wird, und die besagte oxidierbare Oberfläche des festen Metallsubstrats mit der Umwandlungslösung in Kontakt gehalten wird über eine Dauer, welche geeignet ist, um eine Umwandlungsschicht zu bilden, welche von dem besagten Lanthanoid gebildet wird, das über mindestens eine kovalente Bildung an die oxidierbare Oberfläche gebunden ist und sich auf der Oberfläche des festen Metallsubstrats erstreckt.
  8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass die Umwandlungslösung eine Korrosionsinhibitor-Konzentration von zwischen 0,001 Mol/L und 0,5 Mol/L aufweist.
  9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Behandlungslösung aufgebracht wird durch Eintauchen/Einziehen des festen Metallsubstrats in die besagte Behandlungslösung.
  10. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Behandlungslösung durch atmosphärisches Aufsprühen der Behandlungslösung auf die Oberfläche des festen Metallsubstrats aufgebracht wird.
  11. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass die hydroalkoholische Zusammensetzung von Wasser und mindestens einem Alkohol gebildet wird.
  12. Verfahren nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass das Cerkation der Behandlungslösung ausgewählt ist aus der Gruppe, welche gebildet wird von den Cerchloriden und Cernitraten.
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PCT/FR2012/052337 WO2013054064A1 (fr) 2011-10-14 2012-10-12 Procédé de traitement anticorrosion d'un substrat métallique solide et substrat métallique solide traité susceptible d'être obtenu par un tel procédé

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WO2013054064A1 (fr) 2013-04-18
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JP2014528520A (ja) 2014-10-27
CA2851499A1 (fr) 2013-04-18
MX2014004512A (es) 2015-05-11
BR112014008845A2 (pt) 2017-04-18
EP2766508A1 (de) 2014-08-20
US20140255611A1 (en) 2014-09-11

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