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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/48—Stabilisers against degradation by oxygen, light or heat
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
  • C08K13/02—Organic and inorganic ingredients
• • 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
  • 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
  • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
  • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/65—Additives macromolecular
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/66—Additives characterised by particle size
  • C09D7/68—Particle size between 100-1000 nm
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/66—Additives characterised by particle size
  • C09D7/69—Particle size larger than 1000 nm

Definitions

• the present invention relates to coatings for covering the aircraft fuselage. These coatings are intended to form an anticorrosion system, mechanical strength and / or coloring. State of the art
• the first mechanism called “liquid crystal templating” (which can be translated into French by “Texturing by liquid crystals”), implies the existence of a prior crystal-liquid phase before the condensation of inorganic species.
• the formation of the material then results from the diffusion of the inorganic precursors in the inter-micellar spaces of the organic mesophase.
• the second mechanism is based on the phenomenon of cooperative self-assembly, in which the surfactant molecules and the inorganic species combine in a first step to form an intermediate hybrid mesophase.
• sol-gel chemistry hydrolysis-condensation of inorganic precursors and / or organic-inorganic hybrids
• crystal-liquid phase pre- or post-formed
• the properties of use of such materials are intimately related to the release of porosity by removal of the surfactant phase which is generally obtained via chemical extraction processes or by heat treatments at high temperature (500 ° C).
• the mesostructured materials whose porosity has been released are defined as periodically organized mesoporous materials.
• the mesostructured materials synthesized in powder form were most often obtained according to precipitation synthesis methods. Generally, these require an autoclave ripening step often long (12 to 24) and incompatible with continuous production. In addition, the stoichiometry of the initial solution and that of the final material may differ if some of the reagents are found in the supernatant. Finally, with this technique it is difficult to obtain elementary particles that have a regular shape and size.
• the synthesis of materials according to ⁇ firstly involves the preparation of a dilute aqueous or hydro-alcoholic solution, containing inorganic and / or hybrid precursors, catalysts and / or inhibitors of hydrolysis-condensation reactions (respectively, in the case of silicic precursors and transition metal oxides), surfactants and functional molecules and / or nano-objects.
• This solution can then be deposited on a substrate either by dip-, spin- or spray-coating (which can be respectively translated into French by "dip, spin, or spray") to form a film, or atomized in spherical droplets to obtain spherical particles via the aerosol process.
• the material then undergoes an evaporation phase at moderate temperatures (less than 250 ° C.) allowing self-assembly of the surfactants and partial condensation of the inorganic and / or hybrid precursors around the micellar aggregates.
• the material obtained can then undergo a post-treatment to consolidate the inorganic or hybrid phase.
• the evaporation method has several advantages such as better control of the hydrolysis-condensation of the reagents, a control of the particle stoichiometry equal to that of the non-volatile species stoichiometry of the solution.
• the particles described in these articles are not mesostructured but mesoporous.
• the preparation of the particles loaded with corrosion inhibitors was carried out after a long process (48 hours), multi-step synthesis and post-treatments, a process that is difficult to implement with an industrial scale implementation.
• the particles described in these articles were obtained by the conventional route of precipitation and not by atomization of a solution.
• the mesoporous particles have been loaded with corrosion inhibitors using an iterative absorption process in solution, which is a long, constraining, load-limiting process that generates a large quantity of effluents that must be reprocessed.
• the mesostructured matrices have three distinct regions at the nanoscale: (a) the inorganic and / or hybrid network, (b) the aqueous interface composed of M-OH / MO "groups (M being a metal or silicon), of H 2 0 and polar heads of surfactants, and (c) the hydrophobic core of micellar aggregates
• the solubilization of functional molecules in a mesostructured matrix is mainly governed by the following principle: "like dissolves like” (which one can be translated into French as "which resembles itself dissolves") This principle implies that a polar molecule is rather localized either in the inorganic and / or hybrid network (provided that the hybrid part is itself polar) or the aqueous interface, and that an apolar molecule is rather solubilized in the hydrophobic core of the micellar phase.
• this principle is statistical and does not really reflect the diffusion of molecules within mesostructured materials. Indeed, the molecules can migrate from the hydrophobic part of the micelles to the aqueous interface (and vice versa) depending on the thermal agitation medium or chemical reactions (protonation-deprotonation). In addition, the diffusion of the molecules is not only limited to the nanoscale between these three regions but can occur within the mesostructure over a greater distance in a relatively short time (several tens of microns in a few minutes) .
• mesostructured materials Many parameters influence the diffusion of molecules in mesostructured materials such as size, charge, hydrophilic / hydrophobic balance of molecules, intra- or intermolecular interactions, type of mesostructure (lamellar, 2D-hexagonal, vermicular, cubic) , the size of the pores, the presence or absence of surfactants, the nature of the surfactants (cationic, anionic or nonionic), the amount of M-OH / MO " at the interface, the amount of water in the material, the nature of the surface of the pores (inorganic or organically modified), the interconnection between pores, the tortuosity of the network etc.
• a diffuse molecule all the more quickly and easily that the interactions between the matrix and the functional molecule are weak.
• the diffusion of a molecule in a mesostru matrix cturée is not linear but consists of a succession of adsorption-desorption phases and diffusion phases.
• molecules solubilized in the surfactant phase which is assimilable to a solvent
• a coating comprising mesostructured particles can be shaped by several different deposition techniques.
• the best-known techniques are dip-coating (which can be translated in French by “dip-withdrawal"), spin-coating (which can be translated into French). by “spin coating”), coil-coating and roll-coating (which can be translated into French by “laminar coating”), the capillary-coating (which can be translated into French by " capillary deposition "), the doctorblade (which can be translated into French by” deposition by scraping ”) and spray-coating (which can be translated into French by” spray coating ").
• the spray-coating the homogeneous coating from a poorly stable suspension, coating in which the particles will be distributed statistically throughout the thickness of the coating, is the spray-coating, the homogeneity being an important parameter in terms of reproducibility, mechanical properties and anticorrosion activity.
• the spray coating also allows the deposition of coating on parts of large dimensions and complex shapes.
• the present invention aims to remedy all or part of the disadvantages of the state of the art mentioned above.
• the present invention relates, according to a first aspect, to a coating comprising at least one layer comprising micrometric, individualized and mesostructured spherical particles, said particles having been created and loaded with at least one element selected from functional inhibitory molecules.
• corrosion and nano-functional objects corrosion inhibitors by a process comprising non-dissociable and continuous steps in the same nebulization-heating reactor.
• the presence of micrometric, individualized and mesostructured spherical particles makes it possible to preserve the mechanical and barrier properties of the host layer.
• the mesostructured spherical particles whatever their chemical nature, remain in the individualized state and do not form aggregates both in the dry state and when they are dispersed in a matrix.
• Corrosion inhibitors and functional nano-objects that are corrosion inhibitors must be understood to mean any chemical species likely to have an active anticorrosion action and preferably corrosion inhibitors, whether organic or inorganic, in the molecular state, of oligomers or aggregates.
• the process for creating and loading the mesostructured particles included in the coating forming the subject of the present invention comprises the non-separable and continuous stages in the same reactor, as follows:
• the layer comprising the spherical mesostructured particles is a sol-gel based organic-inorganic hybrid hermetic layer or a hermetic primer layer (primer layer).
• This hermetic layer has the advantage of providing a barrier property for corrosion protection.
• the spherical mesostructured particles have the function of providing the active property against corrosion via functional molecules and functional nano-objects.
• the layer comprising the mesostructured spherical particles is a mesostructured matrix comprising at least one element selected from corrosion inhibiting functional molecules and corrosion inhibiting functional nano-objects. This improves the active anti-corrosion property.
• matrix and particles allow an increased diffusion of the functional molecules in the coating and therefore exacerbated anticorrosion properties.
• matrix is chemically of the same nature as the mesostructured spherical particles, it facilitates the incorporation of the mesostructured spherical particles into the matrix, without altering the macroscopic and microscopic properties of the matrix.
• the mesostructured matrix layer is obtained from a suspension comprising at least one element selected from an inorganic precursor and a hybrid organic-inorganic precursor, in macromolecular form.
• a suspension comprising at least one element selected from an inorganic precursor and a hybrid organic-inorganic precursor, in macromolecular form.
• liquid solution comprising one or more precursors of the three-dimensional network of the mesostructured matrix, at a given molar concentration in at least one solvent, the liquid solution also comprises at least one surfactant and optionally at least one element selected from functional corrosion inhibiting molecules and functional nano-objects that inhibit corrosion, depositing the solution on a previously prepared substrate, after stirring and aging of the solution, said deposit can be produced by dip-coating or spray-coating,
• the coatings comprising the mesostructured matrix comprise a sol-gel-based organic-inorganic hybrid hermetic top layer or a hermetic topcoat topcoat.
• This hermetic upper layer provides the barrier property which limits the penetration of aggressive species towards the substrate and the mesostructured matrix as well as the mesostructured spherical particles provide the active property anticorrosion through the functional molecules and functional nano-objects.
• the mesostructured matrix comprises functional organosilanes bearing at least one group selected from an amino group, a sulfide, a carboxyl and a thiol. This allows a selective passivation of the surface of the intermetallic particles of the substrate by means of strong bonds of the covalent or ionocovalent type, thereby limiting the corrosion phenomenon.
• the mesostructured spherical particles incorporated in the coatings have a diameter of between 0.1 and 10 microns. This feature promotes their introduction into a coating layer without modifying the barrier properties. In addition, this characteristic is compatible with the incorporation of the mesostructured spherical particles in a thin coating (thickness of the order of a few microns). In embodiments, the mesostructured spherical particles incorporated in the coating have a sphericity coefficient greater than or equal to 0.75.
• the mesostructured spherical particles incorporated in the coatings exhibit a mesostructure with periodic organic-inorganic organic or inorganic phase segregation or organic-inorganic phase segregation with a periodicity between the 2 phases ranging from 2 to 50 nanometers.
• the periodicity between the two phases is between 2 and 15 nanometers.
• the present invention aims at the use of a coating object of the present invention for protecting light alloys of the aeronautical and aerospace fields.
• the present invention is an aircraft comprising a coating object of the present invention.
• FIG. 1 illustrates coatings comprising at least one layer comprising micrometric, individualized, and mesostructured spherical particles, said particles having been, in a single step, created and loaded with at least one element selected from functional molecules and nanoparticles; functional objects, according to embodiments of the invention.
• Figure 1 illustrates coatings 30 comprising at least one layer having mesostructured spherical particles loaded with molecules and / or functional nano-objects.
• mesostructured spherical particles it is to be understood any particle exhibiting an organized and periodic phase segregation at the mesoscopic scale leading to the existence within said particles of at least one three-dimensional network, which may be inorganic and advantageously d-based.
• oxide (s), organic-inorganic hybrid, and the other phases may be purely organic advantageously based on micellar aggregates of surface-active molecules, organic-inorganic or inorganic hybrid.
• the mesoscopic scale corresponds to a scale ranging from 2 to 50 nanometers.
• Said mesostructured materials are prepared by sol-gel from at least one metal molecular precursor comprising one or more hydrolyzable groups, of formula (1), (2), (3) or (4) defined below, in presence of at least one particular texturing agent as defined below, the texturing agent being retained in the final material.
• Said mesostructured materials are obtained in the form of films and / or in the form of spherical particles as defined above.
• hydrolyzable group is meant a group capable of reacting with water to give a group -OH, which will undergo itself a polycondensation.
• Said metal molecular precursor comprising one or more hydrolyzable groups is chosen from an alkoxide or a metal halide, preferably a metal alkoxide, or an alkynylmetal of formula:
• M represents Al (III), Ce (III), Ce (IV), Si (IV), Zr (IV), the number in parentheses being the valence of the atom M;
• n represents the valence of the atom M;
• x is an integer from 1 to n-1;
• x ' is an integer from 1 to 3;
• Each Z independently of one another, is selected from a halogen atom and a group -OR, and preferably Z is a group - OR;
• 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, ethyl or i-propyl, more preferably 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 -C 4 alkenyl groups, such as vinyl, 1-propenyl, 2-propenyl and butenyl; alkynyl groups, in particular C 2 - 4 groups , such as acetylenyl and propargyl; especially C 6 -C 10 aryl groups, such as phenyl and naphthyl; methacryl or methacryloxy groups (CM O alkyl) such as methacryloxypropyl; epoxyalkyl or epoxyalkoxyalkyl groups in which the alkyl group is linear, branched or cyclic, C 1 -C 0 , and the alkoxy group has 1 to 10 carbon atoms, such as glycidyl and glycidyloxy (C 1
• L represents a ligand complexing monodentate or polydentate, preferably polydentate, for example, a carboxylic acid preferably C 1 -18, such as acetic acid, a ⁇ -diketone preferably C 5-2 o, such as acetylacetone, a ⁇ -ketoester preferably C 5 - 2 o, such as methyl acetoacetate, a ⁇ -ketoamide preferably C 5 - 2 o, such as N-methylacetoacetamide, a-or ⁇ -hydroxyacid preferably C 3 - 2 o, such as lactic acid or salicylic acid, an amino acid such as alanine, a polyamine such as diethylenetriamine (or DETA), or phosphonic acid or a phosphonate; m represents the hydroxylation number of ligand L; and
• R represents a non-hydrolysable functional group chosen from alkylene groups preferably C - 2, for example, methylene, ethylene, propylene, butylene, hexylene, octylene, decylene and dodecylene; alkynylene groups, preferably C 2 -i, for example acetylenylene (- C ⁇ C -), -C ⁇ C -C ⁇ C -, and -C ⁇ C -C 6 H 4 -C ⁇ C - N, N-di (C 2 -C 2 alkylene) groups; -io) amino such as ⁇ , ⁇ -diethyleneamino; bis [N, N-di (C 2 -C 10 alkylene) amino] groups such as bis [N- (3-propylene) -N-methyleneamino]; mercaptoalkylene; C 2 i 0 such that mercaptopropylène; groups (alkylene C 2 i 0 such
• Organosilane types such as: -CH 2 CH 2 -SiMe 2 -C 6 H 4 -SiMe 2 -CH 2 CH 2 -, -CH 2 CH 2 -SiMe 2 -C 6 H 4 -O-C 6 H 4 -SiMe 2 -CH 2 CH 2 - and -CH 2 CH 2 -SiMe 2 -C 2 H 4 -SiMe 2 -CH 2 CH 2 -,
• M is different from Si for formula (2).
• Exemplary compounds of formula (1) there may be mentioned tetra (Ci -4 alkoxy) silanes and the zirconium n-propoxide Zr (OCH 2 CH 2 CH 3) 4.
• organoalkoxysilane of formula (3) there may be mentioned 3-aminopropyltrialkoxysilane (RO) 3 Si- (CH 2 ) 3 -NH 2 , 3- (2-aminoethyl) aminopropyltrialkoxysilane (RO) 3 Si- (CH 2) 3-NH- (CH 2 ) 2 -NH 2, 3- (trialkoxysilyl) propyldiethylenetriamine (RO) 3 Si- (CH 2) 3 -NH- (CH 2) 2 -NH- (CH 2 ) 2 NH 2 ; 3-chloropropyltrialkoxysilane (RO) 3 Si- (CH 2 ) 3 Cl, 3-mercaptopropyltrialkoxysilane (RO) 3 Si- (CH 2 ) 3 SH; azolesorganosilyles of N- (3-trialkoxysilylpropyl) -4,5-dihydroimidazole type, R having the same meaning as above.
• bis-alkoxysilane of formula (4) a bis- [trialkoxysilyl] methane (RO) 3 Si-CH 2 -Si (OR) 3, a bis- [trialkoxysilyl] ethane (RO) 3 Si is preferably used.
• an organic-inorganic hybrid is understood to mean a network consisting of molecules corresponding to formulas (2), (3) or (4).
• amphiphilic surfactant which may be used in the invention as texturizing agents, are ionic amphiphilic surfactants such as anionic or cationic, amphoteric or zwitterionic, or nonionic, and which may be in addition photo- or thermopolymerizable.
• This surfactant can be an amphiphilic molecule or a macromolecule (or polymer) having an amphiphilic structure.
• cationic amphiphilic surfactants there may be mentioned quaternary ammonium salts such as those of formula (I) below, or salts of imidazolium or pyridinium, or phosphonium.
• radicals R 8 to Ru which may be the same or different, represent a linear or branched alkyl group having from 1 to 30 carbon atoms, and X represents a halogen atom such as a chlorine atom or bromine, or sulphate.
• tetraalkylammonium halides such as, for example, dialkyldimethylammonium or alkyltrimethylammonium halides in which the alkyl radical comprises about 12 to 22 carbon atoms , in particular the behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium and 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 1 ) 3 N + -CH 2 -CH 2 -COO " in which each R 2 , identical or different, represents a hydrogen atom or a C 1 -C 20 alkyl group such as dodecyl, and more particularly dodecylamino-propionic acid.
• the molecular nonionic amphoteric surfactants useful in the present invention are preferably C-12-22 ethoxylated linear alcohols having from 2 to 30 ethylene oxide units, or fatty acid esters comprising from 12 to 22 carbon atoms, and sorbitan. It may especially be mentioned as examples those sold under the trademarks Brij ®, Span ® and Tween ® by Aldrich, for example, Brij ® C10 and 78, Tween 20 and Span ® 80 ®.
• Polymeric nonionic amphiphilic surfactants are any amphiphilic polymer having both a hydrophilic character and a hydrophobic character.
• an amphiphilic block copolymer chosen from a copolymer based on poly (meth) acrylic acid, a copolymer based on polydiene, a copolymer based on hydrogenated diene, a copolymer with poly (propylene oxide) base, poly (ethylene oxide) -based copolymers, polyisobutylene-based copolymer, polystyrene-based copolymer, polysiloxane-based copolymer, poly-based copolymer (2-vinyl-naphthalene), a copolymer based on poly (vinyl pyridine and N-methyl vinylpyridinium iodide) and a copolymer based on poly (vinylpyrrolidone).
• 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.
• 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) u and (POE) w and the Poly (alkylene oxide) chains of hydrophobic nature are chains of poly (propylene oxide) denoted (POP) v or chains of poly (butylene oxide), or mixed chains in which each chain is a mixture of several monomers of alkylene oxides.
• a compound of formula (POE) u- (POP) v- (POE) w can be used with 5 ⁇ u ⁇ 106, 33 ⁇ v ⁇ 70 and 5 ⁇ w ⁇ 106 .
• Functional molecules and functional nano-objects of inorganic nature having an anticorrosion action are chosen from corrosion inhibitors comprising rare earths such as the cerium, neodymium (III), praseodymium (III) and / or molybdate salts, vanadates, tungstates, phosphates, Co (III) and Mn (VII) salts.
• corrosion inhibitors comprising rare earths such as the cerium, neodymium (III), praseodymium (III) and / or molybdate salts, vanadates, tungstates, phosphates, Co (III) and Mn (VII) salts.
• CeCl 3 Ce (NO 3 ) 3 , Ce 2 (SO 4 ) 3 , Ce (CH 3 CO 2 ) 3 , Ce 2 (MoO 4 ) 3 , Na 2 MoO 4 NaVO 3 , NaW0 4 -3W0 3, Sr-AI-polyphosphate, zinc phosphate, KH 2 P0 4, Na 3 P0 4, YCI 3 LACI 3, Ce (l0 3) 3, or from particles of magnesium or molybdenum, and silica or alumina nanoparticles, zirconia, BaB 2 O 4 , Na 2 SiO 3 , Na 2 MnO 4 ; cerium oxide, praseodymium oxide, silica, antimony tin oxide, barium sulfate, zinc nitroisophthalate, organophilized calcium strontium phosphosilicate, zinc molybdate and polyphosphate of modified aluminum.
• Functional molecules and functional nano-objects of organic nature having an anticorrosion action are chosen from agents of the azole, amine, mercaptan, carboxylate and phosphonate types; benzotriazole, 2-mercaptobenzothiazole, mercaptobenzimidazole, sodium benzoate, nitrochlorobenzene, chloranyl, 8-hydroxyquinoline, N-methylpyridine, piperidine, piperazine, 1,2-aminoethylpiperidine, N-2- aminoethylpiperazine, N-methylphenotiazine, ⁇ -cyclodextrin, imidazole and pyridine, 2,4-pentanedionate, 2,5-dimercapto, 1,3,4-thiadiazole (DMTD), N, N-diethyl-dithiocarbamate ( DEDTC), 1-pyrrolydine-dithiocarbamate (PDTC) agents formed an anthracene molecule bearing imidazolium groups;
• Said mesostructured spherical particles by the choice of inorganic precursors and / or organic-inorganic hybrids (organosilanes carrying one or more non-hydrolysable functions) and by the presence of an extended surfactant phase behaving like a liquid phase, exhibit a release time controlled molecules and / or functional nano-objects (fast to slow, the duration depending on the composition of the particles 20).
• the process for synthesizing mesostructured spherical particles is a spray drying process (or "spray drying" in English terminology).
• the process for synthesizing the particles consists in atomizing a solution containing the solvent (s) as well as the non-volatile compounds (inorganic precursors and / or organic-inorganic hybrids, the surfactants, the agents anti corrosion).
• the solution is prepared, it is atomized, according to a pneumatic or piezoelectric process, in the form of fine droplets which are transported via a carrier gas (air) in a drying zone whose temperature is below 400 ° C., if necessary. according to a temperature gradient for example of 40 to 400 ° C in a time interval of 1 to 30 seconds, as illustrated in particular in the examples.
• the process of self-organization of mesophase surfactants as well as that of condensation of inorganic precursors and / or organic-inorganic hybrids occurs in this drying zone.
• the residence time of the droplets / particles in the drying zone is of the order of a few seconds (from 1 to 30 seconds).
• the particles are then harvested in a filter.
• the mesostructured spherical particles remain in the individualized state and do not form aggregates both in the dry state and when dispersed in a matrix.
• a particle is not constituted by the aggregation of several smaller sized particles.
• a set of particles 20 may optionally contain particles 20 which do not meet this characteristic, insofar as the non-aggregation criterion is met by at least 50% by number of the particles 20 of the assembly.
• at least 60%, at least 70%, at least 80%, at least 90%, at least 95% by number of the particles of the set considered are individualized.
• the mesostructured particles are spherical, i.e. they have a sphericity coefficient greater than or equal to 0.75.
• the sphericity coefficient is greater than or equal to 0.8, greater than or equal to 0.85, greater than or equal to 0.9, or greater than or equal to 0.95.
• the sphericity coefficient of a particle 20 is the ratio of the smallest diameter of the particle 20 to the largest diameter thereof. For a perfect sphere, this ratio is equal to 1. At least 50% of the particles in number have a sphericity as defined above.
• At least 60%, at least 70%, at least 80%, at least 90%, at least 95% by number of the particles of the set considered have a sphericity as defined above.
• the particle diameter is between 0.1 and 10 micrometers.
• the diameter of the micelles 21 of the mesostructured spherical particles is of the order of 2 to 15 nanometers.
• the particles 20 according to the invention are non-deformable individualized particles.
• the synthesis of the coating object of the invention is carried out according to the sequence of the following steps: a first step consists in synthesizing micrometric, individualized and mesostructured spherical particles, said particles being, in a single step, created and charged with at least one element selected from molecules functional and functional nano-objects.
• a second step corresponds to the production of a suspension 22 comprising reagents composing the layer comprising the mesostructured spherical particles, and the mesostructured spherical particles themselves.
• said heterogeneous suspension 22 is deposited by spray-coating technique (which can be translated, in French by "spray”), dip-coating (which can be translated into French by “immersion” or “soaking”) or by spin-coating (which can be translated into French by "spin”) on a previously prepared substrate 31 or on a conversion layer 32.
• spray-coating technique which can be translated, in French by "spray”
• dip-coating which can be translated into French by "immersion” or “soaking”
• spin-coating which can be translated into French by "spin
• treatment of the deposited coating is carried out with at least one treatment chosen from a heat treatment and a UV-visible irradiation treatment.
• the layer comprising the mesostructured spherical particles may be of different nature according to embodiments of the invention.
• the layer comprising the mesostructured spherical particles is a sol-gel based organic-inorganic hybrid dense layer 33 or a dense layer of primer (primer).
• primer primer
• the term "dense layer” means a layer which does not have mesostructuring, it is a layer hermetically closed to the external environment and which has barrier properties with respect to the electrolytes. Here is meant by dense layer, a hermetic layer. The said layer is therefore waterproof, it does not let through liquids, gases, dust, moisture.
• FIG. 1 the layer comprising the mesostructured spherical particles may be of different nature according to embodiments of the invention.
• the layer comprising the mesostructured spherical particles is a sol-gel based organic-inorganic hybrid dense layer 33 or a dense layer of primer (primer).
• the term "dense layer” means
• the layer comprising the mesostructured spherical particles is a mesostructured matrix comprising molecules and / or functional nano-objects such as those defined above.
• the mesostructured matrix 35 is covered with a sol-gel based organic-inorganic hybrid dense top layer 34 or a dense top top layer 34.
• the functional molecules and / or nano-objects are trapped in micellar aggregates 21 organized to form a mesostructure within the particles 20 and matrix 35 in which the micellar aggregates 21 are trapped.
• the mesostructured matrix is of organic-inorganic hybrid nature.
• organic-inorganic hybrid is understood to mean the same definition as that given above for the hybrid organic-inorganic network of mesostructured spherical particles.
• the hybrid organic-inorganic mesostructured matrix allows the coating to adhere to lower layers such as metal substrates via metal-O-Si or Si-O-Si bonds, and promotes good adhesion of the top layers (primer or paint). ) by organic bonds obtained through the use of hybrid organic-inorganic coupling agents, such as functional organosilanes (formula 3).
• the mesostructured matrix allows selective passivation of the surface of the intermetallic particles of the substrate through linkages. strong covalent or iono-covalent, thereby limiting the phenomenon of corrosion.
• the inorganic portion provides good scratch resistance and extended life while the organic portion increases the flexibility of the coating 30.
• the mesostructured matrix 35 provides cracks-free coatings and is capable of more easily incorporating submicron or micron particles within it, without altering the macroscopic and microscopic properties of said mesostructured matrix.
• the mesostructured matrix is chemically similar in nature to the mesostructured spherical particles, it facilitates the integration of said mesostructured spherical particles into 30.
• the chemical nature of the mesostructured spherical particles, fully compatible with that of the mesostructured matrix of the coating 30, makes it possible to modulate the strength of the bonds between the particles 20 and the mesostructured matrix 35 in order to obtain a coating 30 having improved mechanical properties and barriers.
• the solution is then stirred at 25 ° C for 24 hours. After aging, 1.00 g of Brij®C10 and 0.58 g of BTA are added to the solution. The mixture is then stirred at room temperature (25 ° C.) until a clear solution (about fifteen minutes) is obtained.
• the solution is then atomized into micrometric droplets in a stream of hot gas (air) using a mono-nozzle having an opening of diameter 0.7 mm.
• the flow rate of the solution was set at 0.34 Lh -1 .
• the compressed air flow rate for atomization was set at 357 Lh -1 .
• the air circulation for the aspiration of the atomized droplets was fixed so as to maintain an overpressure of 3.10 3 Pa before the filter.
• TEOS and 27.50 g of a decimolar aqueous solution of AcOH are added in order and with stirring. The solution is then stirred at 25 ° C for 24 hours.
• 0.90 g of Brij®C10 are dissolved in 5 g of EtOH, heating at 40 ° C for 15 minutes can be used to promote the dissolution of Brij®C10, and the two solutions are mixed with stirring.
• 0.3 g of BTA is finally added to the solution.
• 5.24 g of TEOS and 13.50 g of a decimolar aqueous solution of AcOH are added in order and with stirring. The solution is then stirred at 25 ° C for 24 hours.
• Brij®C10 After aging, 0.90 g of Brij®C10 are dissolved in 5 g of EtOH, heating at 40 ° C for 15 minutes can be used to promote the dissolution of Brij®C10, and the two solutions are mixed with stirring. 0.3 g of BTA is finally added to the solution. Alternatively, 5.30 g of TEOS and 18.35 g of a decimolar aqueous solution of AcOH are added in order and with stirring. The solution is then stirred at 25 ° C for 24 hours.
• the air circulation for the aspiration of the atomized droplets was fixed so as to maintain an overpressure of 3.10 3 Pa before the filter. These conditions correspond to travel times along the spray tube close to 3s.
• the setpoint temperature at the inlet of the atomizer was set at 160 ° C and the Exit temperature observed was 90 ° C.
• the particles thus synthesized and recovered on the filter are then kept in an oven at 60 ° C. for 48 hours and then they are stored hermetically in a polypropylene bottle at room temperature.
• the flow rate of the solution was set at 0.34 Lh -1 .
• the compressed air flow rate for atomization was set at 357 Lh -1 .
• the air circulation for the aspiration of the atomized droplets was fixed so as to maintain an overpressure of 3.10 3 Pa before the filter. These conditions correspond to travel times along the spray tube close to 3s.
• the set point temperature of the atomizer was set at 160 ° C and the observed exit temperature was 90 ° C.
• the particles thus synthesized and recovered on the filter are then kept in an oven at 60 ° C. for 48 hours and then they are stored hermetically in a polypropylene bottle at room temperature.
• 0.88 g of Brij®C10 then 0.68 g of Ce (III) are then dissolved in the solution, alternatively, 3.56 g of TEOS and 9.85 g of EtOH, 24.18 g.
• the solution is then stirred at 25 ° C. for 48 hours and after aging, 0.76 g of MTEOS are added to the solution.
• the solution is then stirred for 6 hours at 25 ° C.
• 0.88 g of Brij®C10 then 0.68 g of Ce (III) are then dissolved in the solution, alternatively, 4.44 g of TEOS.
• 24.18 g of a decimolar aqueous solution of HCl are added in the order and with stirring.
• the solution is then stirred at 25 ° C. for 48 hours.
• Characterization of the particles is carried out both on the powder dried in an oven at 60 ° C (scanning electron microscopy - SEM / X-ray diffraction - XRD / thermogravimetric analysis - ATG) but also after a step of calcination under air at 550 ° C for 8 h (scanning electron microscopy - SEM / transmission electron microscopy - TEM / nitrogen volumetry / X-ray diffraction). These materials have a so-called vermicular mesostructure (MET), a low-angle correlation peak (XRD), a mean diameter centered around 900 nm (SEM), a specific surface after calcination of the order of 500 m 2 . g- 1 (nitrogen volumetry) and a pore diameter of 2.5 nm
• Example 5 Preparation of benzotriazole-loaded micron mesostructured particles (BTA) - sol-gel acetic acid (AcOH) catalyst.
• Preparation of the solution In a polypropylene bottle, the following compounds are added in order and with magnetic stirring: 27.5 g of a 0.1 M aqueous solution of AcOH and 5.30 g (that is 1 5 g of silica) of TEOS. The solution is then stirred at 25 ° C for 24 hours to allow the hydrolysis-condensation of TEOS. After aging, 0.53 g of Brij®C10 are dissolved in 5.82 g of ethanol, heating at 37 ° C for 5 minutes can be used to promote the dissolution of Brij®C10 in the hydroalcoholic solution, then this solution is mixed with the silica precursor solution. Finally, 0.31 g of BTA powder is finally added to the solution.
• the silica / Brij / BTA precursor solution is nebulized by the pyrolysis spray process in a reactor so as to obtain a mist of solution droplets.
• the mist is then heated to a so-called drying temperature capable of ensuring the evaporation of the solvent and the formation of the particles.
• the particles then undergo a heating step at a so-called pyrolysis temperature capable of ensuring the transformation of the precursor (s) to form the inorganic part of the three-dimensional network of the particles.
• the maximum temperature of the oven in which the drying and pyrolysis steps take place is set at 150 ° C. in order to preserve the surfactant and the anticorrosion agent.
• the particles are recovered directly on a filter and optionally dried under air.
• the suspension (solution mixture - mesostructured particles) is then deposited on the metal substrate using a pneumatic gravity gun, the air pressure being adjusted to about 0.7 bars.
• the surface is covered in a manner identical to the application of a primer or a paint, and then within a few minutes to 1 hour, the specimens are placed in an oven set at 70 ° C. After 30 minutes, the test pieces are removed and allowed to cool.
• Example 7 Hybrid organic-inorganic dense coating with mesostructured particles.

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• 2014
  • 2014-12-15 FR FR1462409A patent/FR3029835B1/fr not_active Expired - Fee Related
• 2015
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