Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/08—Anti-corrosive paints
• • 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
• • 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
  • 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
  • C23C18/1229—Composition of the substrate
  • C23C18/1241—Metallic substrates
• • 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
  • C23C18/125—Process of deposition of the inorganic material
  • C23C18/1254—Sol or sol-gel processing
• • 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
  • C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
  • C23C18/143—Radiation by light, e.g. photolysis or pyrolysis
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
  • Y02T50/00—Aeronautics or air transport
  • Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
  • Y10T428/249961—With gradual property change within a component
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31652—Of asbestos
  • Y10T428/31663—As siloxane, silicone or silane

Definitions

• the present invention relates to a structure comprising a mesostructured coating for use in aeronautical and aerospace applications.
• protection against corrosion is generally provided by chromium VI surface treatments, for example, by means of a chromic anodic oxidation process, or a conversion layer.
• US 2003/024432 discloses a coating having anti-corrosion properties, prepared sol-gel from an organometallic salt such as an alkoxyzirconium, an organosilane, and one or more compounds carrying a borate, zinc or phosphate function, in the presence of an organic catalyst such as acetic acid.
• organometallic salt such as an alkoxyzirconium, an organosilane, and one or more compounds carrying a borate, zinc or phosphate function
• US Pat. Nos. 6,261,638 and 1,097,259 disclose methods for preventing the corrosion of metals, comprising the application of a treatment solution based on polyfunctional silanes and difunctional silanes comprising in their chain several atoms. sulfur, respectively.
• these materials have the disadvantage of not being micro- or nanostructured, that is, the distribution of the organic and inorganic domains in the material can not be controlled at the micrometric or nanometric scale. This random distribution can lead to non-reproducible properties from one material to another.
• An advantage of the sol-gel process consists in constructing a three-dimensional network from starting precursors under so-called mild conditions, that is to say at a temperature below 200 ° C., and in a water or water / solvent medium. less harmful to the environment than those used for conventional surface treatments.
• the starting precursors generally used in said sol-gel process are metal alkoxides comprising one or more hydrolyzable groups.
• these coatings are prepared from a titanium alkoxide, leading to a photocatalyst material that degrades rapidly when exposed to the sun.
• This control is achieved by means of structures comprising at least one particular mesostructured layer and a metal substrate.
• Hybrid and inorganic mesostructured layers are in particular known and described in the article "mesostructured hybrid organic-inorganic thin films, by L. Nicole et al., J. Mater. Chem. , 2005, 15, 3598-3627.
• These mesostructured layers have a controlled porosity, that is to say a pore size of between 2 and 50 nm, measured for example according to the method of Brunauer, Emmett and Teller (BET), and are structured at the nanoscale .
• BET Brunauer, Emmett and Teller
• sol-gel precursors and surfactant molecules are obtained from sol-gel precursors and surfactant molecules. This particular combination makes possible the construction of an inorganic or hybrid network around the surfactant molecules. A mesostructured material is then obtained, the micelles of surfactant molecules being arranged periodically throughout the material.
• These mesostructured layers may comprise various functionalities that make it possible to confer on a metal substrate (or surface), in particular an alloy of aluminum, titanium or magnesium, or a steel, for example, a protection against corrosion, a resistance to scratches and rubbing, good mechanical strength and / or color and / or constitute a probe for quality control while having good adhesion to the metal substrate.
• these layers can allow the coexistence of several different functionalities and can be deposited by any conventional technique such as, for example, by dip-coating, deposit on spinning substrate (or spin-coating) , spraying, spraying, laminar coating and brush coating.
• the individual components may be designed to have a life time compatible with industrial cycles, for example, greater than or equal to 12 months, and to be mixed just prior to their application.
• Their formulation has the additional advantage of using components compatible with environmental regulations, and in particular to be predominantly in an aqueous medium.
• the subject of the present invention is therefore a structure comprising: at least one mesostructured layer prepared by the sol-gel method from at least one metal molecular precursor of the alkoxide or metal halide type of formula:
• R represents an alkyl group preferably comprising 1 to 4 carbon atoms, such as a methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl or t-butyl group, preferably methyl or ethyl, better still ethyl; each R 'represents, independently of one another, a non-hydrolyzable group selected from alkyl groups, especially C 1-4 , for example, methyl, ethyl, propyl or butyl; alkenyl groups, in particular C 2 -4 alkenyl, such as vinyl, 1-propenyl, 2-propenyl and butenyl; alkynyl groups, especially C 2 -4 , such as acetylenyl and propargyl; aryl groups, in particular C 6-10 , such as phenyl and naphthyl; methacryl or methacryloxy (C 1 -C 10 ) al
• L represents a monodentate or polydentate complexing ligand, preferably polydentate, for example a carboxylic acid such as acetic acid, a ⁇ -diketone such as acetylacetone, a ⁇ -ketoester such as methyl acetoacetate, an ⁇ - or ⁇ -hydroxyacid; such as lactic acid, an amino acid such as alanine, a polyamine such as diethylenetriamine (or DETA), or phosphonic acid or a phosphonate; m is the hydroxylation number of ligand L; and
• R represents a non-hydrolysable functional group chosen from alkylene groups, preferably C 2 -I, e.g., methylene, ethylene, propylene, butylene, hexylene, octylene, decylene and dodecylene; N, N-di (alkylene C 2- io) amino such as N, N- diéthylèneamino; groups bis [N, N-di (C 2- io alkylene) amino] such as bis [N- (3-propylene) -N-methyleneamino]; C 2 -C 10 mercaptoalkylene such as mercaptopropylene, C 2 -C 10 alkylene polysulfide groups such as propylene disulfide or propylene tetrasulfide, and C 2 -C 4 alkenylene groups such as vinylene; especially C 6-10, such as phenylene; the di (C 2- io alkylene)
• a particular embodiment of the present invention is that, during the preparation of the mesostructured layer by sol-gel, the molecular precursor (s) of molecular formula (1), (2), (3) or ( 4) are used in combination with at least one precursor based on silicon, silicon alkoxide type, organoalkoxysilane or silicon halide.
• this or these precursors based on silicon of the silicon alkoxide, organoalkoxysilane or silicon halide type correspond to the following formulas:
• organoalkoxysilane of formula (6) there may be mentioned 3-aminopropyltrialkoxysilane (RO) 3 Si- (CH 3 ) 3 -
• a bis- [trialkoxysilyl] methane (RO) 3 Si-CH 2 -Si (OR) 3 , a bis- [trialkoxysilyl] ethane (RO) 3 Si- is preferably used.
• the structure may further comprise another ingredient such as a particulate oxide or hydroxide precursor, such as cerium oxide or zirconium oxide.
• amphiphilic surfactant (s) which may be used in the invention are ionic amphiphilic surfactants such as anionic or cationic, amphoteric, zwitterionic or nonionic surfactants, and which may also be photo- or thermopolymerizable.
• This surfactant can be an amphiphilic molecule or a macromolecule (or polymer) having an amphiphilic structure.
• cationic amphiphilic surfactants examples include quaternary ammonium or phosphonium salts.
• radicals Rs to Rn which may be identical or different, represent a linear or branched alkyl group containing from 1 to 30 carbon atoms, and
• X represents a halogen atom such as a chlorine or bromine atom, or a sulfate.
• tetraalkylammonium halides such as, for example, dialkyldimethylammonium or alkyltrimethylammonium halides in which the alkyl radical comprises approximately 12 to 22 carbon atoms, in particular behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium, benzyldimethylstearylammonium halides.
• Preferred halides are chlorides and bromides.
• amphoteric or zwitterionic amphiphilic surfactants examples include amino acids such as propionic amino acids of formula (R I 2 ) SN + -CH 2 -CH 2 -COO " in which each R 2 , which is identical or different, , represents a hydrogen atom or a C 1-20 alkyl group such as dodecyl, and more particularly dodecylamino propionic acid.
• the molecular nonionic amphiphilic surfactants that can be used in the present invention are preferably linear ethoxylated C 12-22 alcohols containing from 2 to 30 ethylene oxide units, or fatty acid esters containing from 12 to 22 carbon atoms. carbon, and sorbitan. It may especially be mentioned as examples those sold under the trademarks Brij ®, Span ® and Tween ® by Aldrich, for example, Brij ® 56 and 78, Tween 20 and Span ® 80 ®.
• Polymeric nonionic amphiphilic surfactants are any amphiphilic polymer having both a hydrophilic character and a hydrophobic character.
• the block copolymers comprising two blocks, three blocks of type ABA or ABC or four blocks, and any other amphiphilic copolymer known to those skilled in the art, and more particularly those described in Adv. Mater. , S. Fôrster, M. Antonietti, 1998, 10, 195-217 or Angew. Chem. Int. , S. Forster, T. Plantenberg, Ed, 2002, 41, 688-714, or Macromol. Rapid Common, H. Coolf, 2001, 22, 219-252.
• an amphiphilic block copolymer of the following type is preferably used: copolymer based on poly (meth) acrylic acid, polydiene-based copolymer, hydrogenated diene-based copolymer, poly-based copolymer (propylene oxide), poly (ethylene oxide) copolymers, polyisobutylene copolymer, polystyrene copolymer, polysiloxane copolymer, poly (2-vinyl-naphthalene) copolymer, copolymer based on poly (vinyl pyridine and N-methyl vinyl pyridinium iodide), copolymer based on poly (vinyl pyrrolidone).
• a block copolymer consisting of poly (alkylene oxide) chains is preferably used, each block consisting of a poly (alkylene oxide) chain, the alkylene having a different number of carbon atoms depending on each chain. .
• one of the two blocks consists of a poly (alkylene oxide) chain of hydrophilic nature and the other block consists of a poly (oxide) chain. alkylene) of hydrophobic nature.
• two of the blocks are hydrophilic in nature while the other block, located between the two hydrophilic blocks, is hydrophobic in nature.
• the hydrophilic poly (alkylene oxide) chains are poly (ethylene oxide) chains noted (POE) 11 and (POE) W and the Poly (alkylene oxide) chains of hydrophobic nature are chains of poly (propylene oxide) denoted (POP) V or poly (oxide) chains. butylene), or mixed chains in which each chain is a mixture of several alkylene oxide monomers.
• a compound of formula (POE) u - (POP) v - (POE) W can be used with 5 ⁇ u ⁇ 106, 33 ⁇ v ⁇ 70 and 5 ⁇ w ⁇ 106
• the amphiphilic surfactant (s) are preferably used in an amount ranging from 0.05 to 2 mol% and more particularly from 0.2 to 1 mol% relative to the total number of moles of the molecular metal precursor (s).
• the total number of moles of the molecular metal precursor (s) comprises the total number of moles of the molecular metallic precursor (s) of formulas (1) to (4) and of the possible silicon precursor.
• a latex may also be added during the preparation of the mesostructured layer.
• the mesostructured layer is functionalized, that is to say that it comprises groups imparting macroscopic properties to the substrate, such as corrosion resistance, scratch and friction resistance, mechanical strength and hydrophobic character which can be modulated as desired, and or groups constituting a probe for quality control.
• probe is meant by way of example an optical probe, a pH sensitive probe, a dye or a selective fluorescent probe with specific cations or anions.
• This functionalization results either from the presence in at least one starting molecular metal precursor of formula (2), (3), (4), (6), (7) or (8), formulas, of a group R ' , L and / or R "representing a group which confers a functionality (or group which confers a function on the mesostructured layer), or the addition of at least one functionalizing agent during the preparation of the mesostructured layer or the treatment of the mesostructured layer after obtaining it, with at least one functionalizing agent, or a combination of these three possibilities.
• functionalization agent is understood to mean an agent conferring a function on the mesostructured layer, such as a resistance to corrosion, a resistance to scratching and friction or a mechanical strength, or constituting a fluorescent probe for capturing halogenated compounds, a pH sensitive probe, or a staining agent.
• agents conferring resistance to corrosion By way of examples of agents conferring resistance to corrosion, particular mention may be made of organic anti-corrosion agents of azole types, such as benzotriazole, tolyltriazole and imidazole, of amine types such as aminopiperidine or aminopiperazine, types mercaptan -SH, carboxylates such -. COO "as acetate, or types phosphonates, corrosion inhibitors and inorganic non-oxidizing ions such as molybdates, phosphates, and borates may be used as an agent conferring resistance to scratches and rubbing, a titanium or aluminum alkoxide, or nanoparticles of silica or alumina.
• azole types such as benzotriazole, tolyltriazole and imidazole
• amine types such as aminopiperidine or aminopiperazine
• types mercaptan -SH carboxylates such -.
• agent conferring a mechanical strength particular mention may be made of zirconia oxide.
• the agent constituting a fluorescent probe for capturing halogenated compounds may consist of an anthracene molecule carrying imidazolium groups.
• a pH-sensitive probe methyl orange or phenolphthalein may be used as the constituting agent.
• a dye-giving agent there may be mentioned rhodamine, fluorescein, quinizarin, methylene blue and ethylvinol.
• the starting components are added in the following order during the preparation of the mesostructured layer:
• the structure can comprise several mesostructured layers, for example from 2 to 10 layers, whose porosities constitute a gradient, that is to say, for example in the case of four mesostructured layers having respective porosities P 1, P 2, P 3 and P4 between 2 and 50 nm, P 1> P2> P3> P4, the layer having a porosity P 1 being in direct contact with the substrate.
• the structure comprises in a single mesostructured layer, a porosity gradient.
• the metal substrate that can be used in the present invention is preferably titanium, aluminum or one of their respective alloys, such as, for example, TA6V titanium, aluminum of the 2000 family, more particularly the plated or unplated Ai 2024 aluminum of the 7000 family, more particularly AI 7075 or 7175 and aluminum of the 6000 or 5000 family, or of stainless steel, such as for example NCD 16 or 15-5 PH, or magnesium alloy.
• TA6V titanium aluminum of the 2000 family
• the plated or unplated Ai 2024 aluminum of the 7000 family more particularly AI 7075 or 7175 and aluminum of the 6000 or 5000 family
• stainless steel such as for example NCD 16 or 15-5 PH, or magnesium alloy.
• the mesostructured layer is deposited by means of simple techniques to be carried out on the metal substrates, for example by soaking-shrinking, deposition on spinning substrate (or spin-coating), spraying, spraying, laminar coating or brush coating, and preferably by spraying.
• these techniques use products that are compatible with the environment.
• the structures thus obtained exhibit, in particular, corrosion resistance, scratch and friction resistance, coloration and / or hydrophobicity which can be modulated as desired, good adhesion being observed between the mesostructured layer (s) and the metal substrate.
• the structure further comprises at least one dense layer prepared by sol-gel route, as a layer described in French Patent Application No. 2,899,906.
• dense layer is meant a layer having no porosity at the micrometer scale visible by scanning electron microscope (SEM), and more particularly having a porosity of less than 1 micron, measured according to the BET method.
• the dense layer is especially prepared by sol-gel from at least one alkoxide or halide metal or silicon as defined above.
• Said additional dense layer preferably comprises elementary nanoblocks (or nanobuilding blocks (NBB)) and a polymer or hybrid organic / inorganic matrix.
• the elementary nanoblocks may be in the form of clusters or nanoparticles, preferably nanoparticles of size ranging from 2 to 100 nm, better still from 2 to 50 nm, and even more preferably from 2 to 20 nm, the diameter of these nanoparticles being measured by X-ray diffraction and small-angle X-ray scattering, transmission (or TEM) microscopy or light scattering.
• These elementary nanoblocks are essentially based on at least one metal oxide, for example an oxide of aluminum, cerium III or IV, silicon, zirconium, titanium or tin.
• a first method for synthesizing these elementary nanoblocks consists of synthesizing them from metal salts by precipitation.
• Complexing agents may be introduced into the reaction medium to control the size of the elementary nanoblocks formed and ensure their dispersion in the solvent by functionalization of 80 to 100% of the surface of the nanoblocks with monodentate or polydentate complexing agents, such as, for example, carboxylic acid, ⁇ -diketone, ⁇ -ketoester, ⁇ - or ⁇ -hydroxy acid, phosphonate, polyamine and amino acid.
• monodentate or polydentate complexing agents such as, for example, carboxylic acid, ⁇ -diketone, ⁇ -ketoester, ⁇ - or ⁇ -hydroxy acid, phosphonate, polyamine and amino acid.
• the weight ratio between the mineral and organic components is in particular between 20 and 95%.
• the elementary nanoblocks can also be obtained from at least one metal alkoxide or metal halide via hydrolytic or non-hydrolytic processes.
• a hydrolytic process the controlled hydrolysis of at least one metal alkoxide precursor or metal halide of general formula is carried out:
• Mi represents Al (III), Ce (III), Ce (IV), Si (IV), Zr (IV), Ti (IV) or Sn (IV), preferably Zr (IV) or Ce (IV), the the parenthetical number being the valency of the metal atom, nor is the valence of the M 1 atom, xi is an integer from 1 to n 1, Z 1 represents a halogen atom such as F, Cl, Br and I, preferably
• R 1 represents an alkyl group preferably comprising 1 to 4 carbon atoms, such as a methyl, ethyl, n-propyl, i-propyl or butyl group, preferably methyl or ethyl;
• R 1 ' represents a non-hydrolyzable group selected from alkyl groups including C 1-4 , for example, methyl, ethyl, propyl or butyl; alkenyl groups, in particular C 2-4 alkenyl, such as vinyl, 1-propenyl, 2-propenyl and butenyl; alkynyl groups, especially C 2-4 , such as acetylenyl and propargyl; aryl groups, especially C 6-10 , such as phenyl and naphthyl; methacryl or methacryloxy (C 1-10 alkyl) groups such as methacryloxypropyl; and epoxyalkyl or epoxyalkoxyalkyl groups in which the alkyl group is linear,
• controlled hydrolysis is meant a limitation of the growth of the species formed by controlling the amount of water introduced into the medium and possibly by introducing a complexing agent of the metallic central atom, in order to reduce the reactivity of the precursors .
• the elementary nanoblocks preferably in the form of amorphous or crystalline nanoparticles, can be functionalized on the surface. Their functionalization is carried out either directly during their synthesis, or during a second step following their synthesis, in the presence of a functionalization agent for NBB, and preferably during a second step. We speak respectively of pre- or post-functionalization.
• the post-functionalization can be carried out chemically, by choosing a difunctional molecule as functionalizing agent for NBB, one of whose functions has an affinity for the surface of the elementary nanoblock and the other function will be able to interact with the matrix but will not present any affinity for the surface of the elemental nanoblock.
• the chemical functionalization thus makes it possible to modify the surface of the nanoblocks, in particular by simply mixing a solution containing the elementary nanoblocks with a solution containing the functionalizing agent for NBB.
• Examples of functional groups having an affinity for the surface of the nanoblock include, for example, a carboxylic acid function, a diketone function or a phosphate or phosphonate function.
• functions that can interact with the matrix include primary, secondary or secondary amine groups.
• tertiary such as C 1 -C 5 alkylamino
• polymerizable functions such as vinyl, acrylate or methacrylate.
• di-functional molecules used as functionalizing agent for NBB mention may be made in particular of 6-aminocaproic acid and 2-aminoethylphosphonic acid.
• the degree of functionalization is preferably greater than 50%, more preferably greater than 80%.
• the elementary nanoblocks are introduced into an inorganic / organic polymer or hybrid matrix, preferably a hybrid of the sol / gel type, better still based on silica, and even more preferably consisting of silica or silica / oxide. of zirconium.
• This matrix will serve as a connector through which the elementary blocks will form a three-dimensional network.
• the inorganic / organic hybrid matrices are especially obtained by polycondensation of at least two metal alkoxides or metal halides in the presence of a solvent, and optionally a catalyst.
• the metal alkoxides or metal halides employed are especially chosen from those having the general formulas:
• n 2 represents the valence of the metal atom M 2 , preferably 3, 4 or 5;
• x 2 is an integer ranging from 1 to n 2 - 1;
• M 2 represents a metal atom of valence III such as Al; a metal atom of valence IV such as Si, Ce, Zr and Ti; or a metal atom of valence V such as Nb.
• Z 2 represents a hydrolyzable group chosen from halogen atoms, for example F, Cl, Br and I, preferably Cl and Br; preferably C 1-4 alkoxy groups, such as methoxy, ethoxy, n-propoxy, i-propoxy and butoxy; aryloxy groups, in particular C 6-10 , such as phenoxy; especially C 1-4 acyloxy groups, such as acetoxy and propionyloxy; and C 1-10 alkylcarbonyl groups such as acetyl.
• Z 2 represents an alkoxy group, and more particularly an ethoxy or methoxy group;
• R 2 represents a monovalent non-hydrolyzable group selected from alkyl preferably Ci-4, for example, methyl, ethyl, propyl and butyl; alkenyl groups, especially C 2-4 alkenyl groups, such as vinyl, 1-propenyl, 2-propenyl and butenyl; alkynyl groups, especially C 2-4 such as acetylenyl and propargyl; aryl groups, especially C 6-10 , such as phenyl and naphthyl; methacryl and methacryloxy (C 1 -C 10 ) alkyl groups such as methacryloxypropyl; and epoxyalkyl or epoxyalkoxyalkyl groups in which the alkyl group is linear, branched or cyclic, C 1 -C 10 , and the alkoxy group has 1 to 10 carbon atoms, such as glycidyl and glycidyloxy (C 1 -C 10 alkyl) .
• R 2 is
• R 3 represents a divalent non-hydrolyzable moiety selected from alkylene groups, preferably Ci-4, for example, methylene, ethylene, propylene and butylene; alkenylene groups, especially C 2-4 alkenylene, such as vinylene, 1-propenylene, 2-propenylene and butenylene; alkynylene groups, especially C 2-4 such as acetylenylene and propargylene; arylene groups, in particular C 6-10 , such as phenylene and naphthylene; methacryl and methacryloxy (C 1 -C 10 alkyl) groups such as methacryloxypropyl; and epoxyalkyl or epoxyalkoxyalkyl groups in which the alkyl group is linear, branched or cyclic, C 1 -C 10 , and the alkoxy group contains from 1 to 10 carbon atoms.
• alkylene groups preferably Ci-4, for example, methylene, ethylene, propylene and butylene
• R 3 preferably represents a group methylene or glycidyloxy (C 1 -C 10 alkyl) such as glycidyloxypropyl;
• the solvent used in the preparation of the matrix consists mainly of water. Preferably, it comprises 80 to 100% by weight of water relative to the total weight of the solvent, and optionally a C 1-4 alcohol, preferably ethanol or
• the catalyst is preferably an acid, more preferably acetic acid, or CO 2 .
• At least one additive may optionally be added, either during the preparation of the elementary nanoblocks, or during the mixing of the functionalized elementary nanoblocks and the matrix, or during these two steps.
• the additives that can be used in the invention include surfactants for improving the wettability of the soil on the metal substrate, such as the fluorinated nonionic polymers sold under the trademarks FC 4432 and FC4430 by the company 3M; colorants, for example rhodamine, fluorescein, methylene blue and ethyl-violet; crosslinking agents such as diethylenetriamine (or DETA); coupling agents such as aminopropyltriethoxysilane (APTS); nanopigments, or mixtures thereof
• Said dense layer preferably comprising elementary nanoblocks and an organic / inorganic hybrid matrix, is obtained in particular on the one hand: by preparing the elementary nanoblocks, in particular by a hydrolytic process or not as described above, and possibly functionalizing them, on the other hand - by preparing the matrix, and then mixing the optionally functionalized elementary nanoblocks and the matrix.
• the mesostructured layer is preferably in direct contact with the substrate and thus acts as nanoresist of active compounds.
• the structure comprises a multilayer coating comprising at least one mesostructured layer as described above, more particularly at least two layers which comprise at least one mesostructured layer and optionally at least one dense layer as described above, preferably from 2 to 10, more preferably from 2 to 5 layers.
• the total thickness of this multilayer coating preferably varies from 1 to 10 ⁇ m.
• Another object of the present invention is a method for preparing a structure as defined above, comprising the steps of: (a) preparing a sol-gel material by hydrolyzing-condensation of at least one molecular metal precursor of formula (1), (2), (3) or (4) as defined above, optionally in combination with at least one alkoxide or silicon halide of formula
• step (b) depositing the material obtained in step (a) on a metal substrate, for example by soaking-shrinking, depositing on a rotating substrate (or spin-coating), spraying, spraying, laminar coating or brush coating,
• step (e) can be carried out, for example, by preparing a solution containing the functionalizing agent and then impregnating the structure obtained in step (c) or (d) by soaking in said solution for a period of time. from a few minutes to a few hours.
• the functionalizing agent is preferably used in an amount ranging from 1 to 20% by weight relative to the total weight of the solution.
• the preparation of the sol-gel material in step (a) is accomplished by adding the starting components in the following order:
• the amphiphilic surfactant (s) are preferably used in an amount ranging from 0.05 to 2 mol% and more particularly from 0.2 to 1 mol% relative to the total number of moles of the molecular metal precursor (s).
• the subject of the invention is also the use of the structure according to the invention for improving the resistance to corrosion, scratching and friction, the mechanical strength, the probe, the coloration and / or the hydrophobic character of a metal substrate in the aeronautical or aerospace field. The invention and the advantages it brings will be better understood thanks to the examples given below as an indication.
• a precursor mixture solution was prepared. 0.7 g of ZrCU are added to 55.5 g of ethanol with stirring at room temperature. Then 5.62 g of tetraethoxysilane (TEOS) was added dropwise.
• TEOS tetraethoxysilane
• TMOS tetramethoxysilane
• DMDES dimethyldiethoxysilane
• a second type of NBB was further added in the form of a mixture of a 70% tetrapropoxyzirconium (TPO 2) solution in propanol / CH 3 COOH / H 2 O in a weight ratio of 1: 1. 6g / 4.5g, previously stirred for 30 minutes.
• TPO 2 70% tetrapropoxyzirconium
• the final solution was stirred at room temperature for 30 minutes, then 7.96 g of (3-trimethoxysilylpropyl) diethylenetriamine was added dropwise as a crosslinking agent, and let the solution stand for 15 hours at room temperature with vigorous and regular stirring.
• Rhodamine B was added to the solution in such a quantity that its concentration in the final solution was about 10 -3 M.
• a precursor mixture solution was first prepared. 0.7 g of ZrCU are added to 55.5 g of ethanol with stirring at room temperature, then 5.60 g of TEOS are added dropwise. Was used as the surfactant amphiphilic triblock copolymer sold under the trademark Pluronic ® F 127 was added
• the films were stored at room temperature (20-22 ° C.) and high humidity (50%). for 12 hours. After aging, the coating was thermally treated at 250 ° C. for 1 hour to remove the surfactant and then treated in a UV / O 3 oven for 15 minutes.
• the mesostructured coating was then functionalized by immersing the treated layer in an aqueous solution of 0.01 M mercaptosuccinic acid, with stirring for several hours. After immersion, the layer was rinsed with water and dried in air.
• this first mesostructured layer can also be done in a single step (or "one pot"), namely that the surfactant is preserved and the mercaptosuccinic acid is introduced directly into the solution.
• the shrinkage speed was set at 0.68 cm. s "1. was then densified deposition in an oven at 6O 0 C for 2 hours.
• a treatment solution was prepared by adding 0.1 mol of the mixture of the two metal chlorides YCl 3 and ZrCU (with
• the film was kept at room temperature (20-22 ° C.) and high humidity (> 50%) for 12 hours. After aging, the film was densified at 110 ° C. for 1 hour.
• a film was deposited on a metal substrate whose surface was previously prepared as indicated in Example 1, by soaking-removing said substrate in composition 4, with a withdrawal rate of 0.28 cm.s -1 , under controlled ambient conditions
• the shrinkage speed was set at 0.68 cm. s "1. was then densified deposition in an oven at 60 0 C for 2 hours.
• coatings in the form of films having total thicknesses ranging from 500 nm to several ⁇ m, more particularly from 1 to 6 ⁇ m, and preferably between
• These films have a good stability of interfaces, savo ir between the deposited layer and the metal substrate, and between the deposited layer and the primary paint deposit, and good resistance to mechanical deformation such as shock and bending.
• the corrosion resistance with or without paint is at least comparable to that of the chromated layers, or even better in some cases than those of the chromated layers.

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• 2006
  • 2006-10-02 FR FR0608614A patent/FR2906539B1/fr not_active Expired - Fee Related
• 2007
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