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
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
  • B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
  • B01J2/04—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops in a gaseous medium
• • 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
  • C09D5/086—Organic or non-macromolecular 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
  • C09D7/48—Stabilisers against degradation by oxygen, light or heat
• • 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
  • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres

Definitions

• the present invention relates to spherical particles, mesostructured, spontaneously individualized, and comprising anticorrosion agents.
• the invention also relates to a process for preparing these particles.
• the properties conferred on the material by the nano and / or microparticles are generally related to the properties of the particles themselves, such as their morphological, structural and / or chemical properties.
• the properties conferred on the material may also originate from agents incorporated into the body. particles.
• Particles of spherical morphology are particularly interesting in different fields.
• the particles which are said to be spherical are often either aggregates of non-spherical particles, the aggregate having itself a shape approaching a sphere, or have an unsatisfactory sphericity.
• Various methods have been developed to optimize the sphericity of the synthesized particles. Most of these methods are optimized for a single type of particles, for example a chemical type (silica particles for example) or a morphology (hollow particles for example).
• the particles may have different structures.
• they can be full, hollow, porous, non-porous.
• they can be mesostructured, that is to say have an organized and periodic phase segregation at the mesoscopic scale, that is to say between 2 and 50 nm, leading to the existence within the particles of at least one three-dimensional network, which may be inorganic, organic-inorganic hybrid, and the other phases may be purely organic, organic-inorganic or inorganic hybrid.
• the dispersion of particles in a matrix is also a known technique for conferring a property on said matrix.
• pigments can be dispersed in matrices to impart color properties.
• the nature of the particles, their surface properties, and possibly their coating must be optimized to obtain a satisfactory dispersion in the matrix.
• the optimization of the dispersibility of the particles in the matrix will depend both on the nature of the particles and the nature of the matrix. It is important to be able to homogeneously disperse the particles in the matrix, in order to homogeneously distribute the desired property in the entire volume of the matrix. When the particles agglomerate in the matrix, the desired properties are not conferred homogeneously on the matrix and the result obtained is not satisfactory.
• the Applicant has developed a simple process for preparing perfectly spherical micrometric and mesostructured particles of different types of chemicals, containing anticorrosive agents. Surprisingly, the particles obtained by this process, 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.
• the process makes it possible to obtain mesostructured particles, which enables the anticorrosive agents to be particularly effective.
• the process according to the invention makes possible a higher loading rate of anti-corrosion agents than conventional methods by precipitation or impregnation in post-treatment.
• the process according to the invention makes it possible to obtain micron and mesostructured spherical particles loaded with anti-corrosion agents, the formation of the particles, their mesostructuration and the incorporation of anticorrosion agents being concomitant.
• the first object of the present invention is a set of spherical and micrometric particles, characterized in that the particles are mesostructured and individualized, and in that they comprise anticorrosion agents.
• Another object of the invention is a material comprising a set of particles according to the invention dispersed substantially homogeneously in a matrix.
• the invention also relates to a method for preparing a set of particles according to the invention.
• the invention also relates to a method for preparing a material according to the invention, comprising contacting a matrix with a set of particles according to the invention.
• FIG. 1 TEM image of silica particles loaded with BTA of Example 1 A - scale 2 ⁇ - mean diameter 0.71 ⁇ ⁇ 0.34 ⁇
• FIG. 2 TEM image of silica particles loaded with BTA of Example 1A at 20 nm scale
• FIG. 4 TEM image of silica particles loaded with BTA of Example 1B-2 ⁇ m scale-Average diameter 0.86 ⁇ ⁇ 0.30 ⁇
• FIG. 5 TEM image of silica particles loaded with BTA of Example 1B - 20 nm scale
• FIG. 7 TEM image of silica particles loaded with 8 HQ of Example 2, scale 0.5 ⁇ - mean diameter 0.76 ⁇ ⁇ 0.43 ⁇
• FIG. 8 TEM image of silica particles loaded in 8HQ of example 2, scale 0.5 ⁇ - mean diameter 0.76 ⁇ ⁇ 0.43 ⁇
• FIG. 9 Intensity scattered at small angles as a function of the wave vector by GISAXS of Example 2
• Figure 10 Schematic representation of a reactor adapted for implementing the method according to the invention.
• the first object of the present invention is a set of spherical and micrometric particles, characterized in that the particles are mesostructured and individualized and in that they have incorporated anti-corrosion agents.
• a set of individualized particles refers to a set of particles in which the particles are not aggregated, i.e. each particle of the set is not bound to other particles by strong chemical bonds such as covalent bonds.
• the set of particles according to the invention may optionally contain particles that do not meet this characteristic, insofar as the non-aggregation criterion is met by at least 50% by number of the particles 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.
• a particle of the assembly according to the invention is not constituted by the aggregation of several particles of smaller size. This can be clearly visualized for example by microscopy studies, in particular by scanning electron microscopy or transmission. This means that the particles according to the invention can consist only of domains of size significantly smaller than that of the particles according to the invention.
• a particle according to the invention is preferably formed of at least two domains.
• a domain is made of material having the same chemical nature and the same structure, which can be punctual or continuously extended within the particle.
• the atomization techniques conventionally used in the art generally provide aggregated nonspherical particles.
• the objects that are formed by these aggregates of particles can be spherical.
• the particles according to the invention are spherical, that is to say 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 is the ratio of the smallest diameter of the particle to the largest diameter of the particle. For a perfect sphere, this ratio is equal to 1.
• the sphericity coefficient can be calculated for example by measuring the aspect ratio by means of any software adapted from images, for example images obtained by microscopy, in particularly scanning electron microscopy or in transmission, particles.
• the invention relates to a set of particles as defined above.
• the assembly may optionally contain particles that do not have the required sphericity criteria insofar as the number average sphericity on all the particles meets the criteria set in the present invention.
• the term "set of spherical particles” denotes a plurality of particles of which 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 particles according to the invention are micrometric, that is to say that the particle diameter is between 0.1 and 600 microns, in particular between 0.1 and 100 microns. In a preferred embodiment, it is between 0.5 and 20 microns or between 1 and 15 microns.
• the average particle diameter of a set, the standard deviation and the size distribution in particular can be determined by statistical studies from microscopy images, for example scanning electron microscopy or transmission.
• the above diameter values may correspond to the average particle diameter in number, even though some of the particles in the set have diameters outside this range.
• all the particles of the population have a diameter as defined above.
• the relative standard deviation of the particle size in a population of particles according to the invention is less than or equal to 25%, preferably less than or equal to 20%.
• the size distribution of the particles in the set of particles according to the invention can be monomodal or multimodal.
• micrometric particles in the present invention makes it possible to promote the particle dispersion properties, since they are not too large (the sedimentation is thus minimized), and not to have the disadvantages (difficulties of implementation, toxicity , ...) nanoparticles. In addition, this makes it possible to have thin corrosion protection layers (for example less than 50 microns).
• particle is meant in the present invention a particle whose three-dimensional network is constituted at least in part by an inorganic component, that is to say that is, that is not derived from carbon chemistry (except CO3 2 " ).
• the particles according to the invention are inorganic or hybrid (mixture of inorganic and organic components) . The chemical diversity of the inorganic components is well known in the art.
• the inorganic components may especially be metals (or alloys), metal oxides, silicates, phosphates (or apatite), borates, fluorides, carbonates, hydroxycarbonates, vanadates, tungstates. , sulfides and / or oxysulfides, optionally combined with organic compounds such as, for example, latices, carboxylates, phosphonates, amines, ⁇ -diketonates, this list being in no way limiting. may include oxides of metal or semiconductor elements, such as silica, zinc oxide, magnesium oxide, titanium dioxide, alumina, barium titanate or n mixture of these.
• the inorganic components may also include transition metals such as copper, zinc or iron, or rare earths such as yttrium or lanthanides, and / or derivatives thereof such as oxides.
• the inorganic components according to the invention may optionally comprise at least one dopant, such as, for example, aluminum, erbium, europium or ytterbium.
• the dopant is in a proportion of not more than 10% by weight, preferably not more than 5% by weight, in particular not more than 2% by mass.
• the particles according to the invention may comprise a minimum proportion, for example less than or equal to 5% by weight, of contaminants which may have a chemical nature different from that of said particles.
• the inorganic components are alumina, in particular amorphous or crystalline alumina, boehmite, silica, in particular amorphous silica, zinc oxide, in particular hexagonal, optionally doped, for example doped with aluminum, copper oxide, titanium dioxide, in particular anatase or rutile, mixed oxide of titanium and silicon, in particular anatase , montmorillonite, in particular monoclinic, hydrotalcite, in particular hexagonal, magnesium dihydroxide, in particular hexagonal, magnesium oxide, yttrium oxide, in particular cubic oxide, optionally doped with europium and / or erbium and / or ytterbium, cerium dioxide, copper calcium titanate, barium titanate, iron oxide, preferably in hematite form, magnesium sulfate,
• the particles according to the invention are composed of metal oxide, preferably alumina, in particular of amorphous or crystalline alumina, of boehmite, or of silica, in particular of amorphous silica.
• the inorganic component comprises several chemical elements, preferably from 2 to 16 different chemical elements, this number of elements not taking into account the elements O and H possibly included in the inorganic component. It is then heterogeneous inorganic components, that is to say which comprise various elements whose stoichiometry is preferably controlled by the synthesis method.
• the heterogeneous inorganic components can either comprise several chemical elements (except O and H), preferably all the chemical elements (except O and H) constituting the inorganic component, within the same domain, or comprise domains each formed of a single chemical element (except O and H).
• each domain of the heterogeneous inorganic component comprises a single chemical element (except O and H).
• the particles according to the invention are mesostructured, that is to say that they have an organized and periodic phase segregation at the mesoscopic scale, that is to say between 2 and 50 nm, leading to the existence within the particles of at least one three-dimensional network, which may be inorganic or organic-inorganic hybrid, and the other phases may be purely organic, organic-inorganic or inorganic hybrid.
• the three-dimensional network of which the particles are composed is constituted at least in part by a metallic component, possibly an organic-inorganic hybrid. This component can be obtained by sol-gel from at least one metal molecular precursor comprising one or more hydrolyzable groups of formulas (1), (2), (3) or (4) defined below.
• one of the phases of which the particles are composed is constituted at least in part by an organic liquid crystal phase.
• One or more amphiphilic surfactant (s) may be used in the invention as precursors of the liquid-crystal phase.
• These surfactants are preferably ionic amphiphilic surfactants, such as anionic or cationic, amphoteric or zwitterionic, or nonionic surfactants, and may be furthermore photo-or thermopolymerizable.
• This surfactant can be an amphiphilic molecule or a macromolecule (or polymer) having an amphiphilic structure.
• the surfactants preferably used in the present invention are described below.
• cationic amphiphilic surfactant there may be mentioned quaternary ammonium salts such as those of formula (I) below, or imidazolium or pyridinium salts, or phosphonium.
• radicals Rs to Ru which may be identical or different, represent a linear or branched alkyl group containing from 1 to 30 carbon atoms
• X represents a halogen atom such as a chlorine atom or a bromine, or a sulphate.
• tetraalkylammonium halides such as, for example, dialkyldimethylammonium or alkyltrimethylammonium halides in which the alkyl radical contains from about 12 to 22 carbon atoms, in particular in particular behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium, benzyldimethylstearylammonium halides.
• Preferred halides are chlorides and bromides.
• amphoteric or zwitterionic amphiphilic surfactant the amino acid may be cited as the amino-propionic acids of formula (Ri2) 3N + -CH2-CH2-COO "wherein each R12, identical or different, represents a hydrogen atom, hydrogen or a C 1 -C 20 alkyl group such as dodecyl, and more particularly dodecylamino-propionic acid.
• nonionic molecular amphiphilic surfactants that may 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 ® 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, a copolymers based on poly (ethylene oxide), a polyisobutylene-based copolymer, a polystyrene-based copolymer, a polysiloxane-based copolymer, a copolymer based on poly (2-vinylnaphthalene), 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.
• POP polypropylene oxide
• 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 particles according to the invention comprise or contain anticorrosion agents.
• the anticorrosive agents can be organic agents or inorganic compounds. Their incorporation is carried out during the preparation of the particles.
• the corrosion inhibitors of inorganic nature are preferably chosen from corrosion inhibitors comprising rare earths, such as the cerium, neodymium (III), praseodymium (III) salts, and / or molybdates, vanadates, tungstates, phosphates, salts of Cobalt Co (III), Manganese Mn (VII).
• CeCb, Ce (N0 3 ) 3 , Ce 2 (S0 4 ) 3 , Ce (CH 3 CO 2 ) 3 , Ce 2 (MoO 4 ) 3 , Na 2 MoO 4 NaVo 3 , NaWO 4 - 3WO 3 may especially be mentioned.
• the anticorrosion agents of organic nature are preferably chosen from agents of the azole, amine, mercaptan, carboxylate and phosphonate types. Mention may in particular be made of benzotriazole (BTA), 2-mercaptobenzothiazole, mercaptobenzimidazole, sodium benzoate, nitrochlorobenzene, chloranyl, 8-hydroxyquinoline, N-methylpyridine, piperidine, piperazine and 1,2-mercaptobenzimidazole.
• BTA benzotriazole
• 2-mercaptobenzothiazole 2-mercaptobenzothiazole
• mercaptobenzimidazole sodium benzoate
• nitrochlorobenzene chloranyl, 8-hydroxyquinoline, N-methylpyridine, piperidine, piperazine and 1,2-mercaptobenzimidazole.
• the particles according to the invention can be loaded with one or more organic and / or inorganic anticorrosion agents.
• organic anticorrosive agents When there are several anti-corrosion agents in the same particle, it may be a mixture of organic anticorrosive agents, a mixture of inorganic anticorrosion agents or a mixture of organic and inorganic anticorrosion agents.
• the anticorrosion agents may be present in the particles according to the invention in the form of nanoparticles or not.
• organic anticorrosion agents their encapsulation in particles according to the invention makes it possible to formulate these agents in hydrophilic media and thus make these organic agents active in various types of matrices, and in particular hydrophilic matrices. This can also help protect the anticorrosive agents, especially the organic agents, when they are used in an aggressive environment.
• the particles according to the invention have anticorrosion agents whose quantity may vary to a large extent, which depends in particular on the size of the particles, the geometric characteristics of the nanoreggregation of phases (tortuosity, shrinkage, type of mesophases: vermicular, cubic or 2D-hexagonal for example), the chemical nature of the interface between the three-dimensional network and the other phases, and also the desired application.
• the ratio of anticorrosive agents can vary from 5 to 90% by volume relative to the total volume of particles + anti-corrosion agents, preferably from 10 to 80% by volume, in particular from 10 to 50%.
• the type of nanosegregation as well as the chemical nature of the three-dimensional network interface - other phases of the particles according to the invention make it possible to control in particular the release rate of the anticorrosion agent.
• the release rate of the agent may also depend on the matrix itself.
• the release rate of the anticorrosion agent may also depend on a stimulus.
• a post-treatment step which consists in sealing, at least momentarily, the particles, which is intended in particular to prolong the release of the anticorrosion agent.
• the particles according to the invention may have degradable shells, in particular, by the action of an external stimulus of pH (by dissolution), mechanical (brittle shell), thermal (shell melting by temperature rise) type. or optical (shell that breaks up under irradiation).
• Another object of the invention is a material comprising a set of particles according to the invention, dispersed substantially homogeneously in a matrix.
• matrix designates any material that can advantageously benefit from the inclusion of particles according to the invention. It may be in particular solid or liquid matrices, whatever the viscosity of the starting liquid matrix.
• the matrix is a flexible, rigid, or solid matrix used as a coating, for example a metal, ceramic or polymeric matrix, in particular a polymeric matrix of paint type, sol-gel layers, varnish or one of their mix.
• the matrix can thus be deposited on a substrate that can corrode, such as a metal substrate.
• the inclusion of the particles according to the invention in a matrix makes it possible to confer the anticorrosion property on the matrix.
• the inclusion of the particles in the matrix can be carried out by the techniques conventionally used in the art, in particular by mechanical stirring when the matrix is liquid.
• the material according to the invention may especially be in the form of powder, beads, pellets, granules, films, foam and / or extrudates, the shaping operations being carried out by the conventional techniques known from the art. skilled person.
• the process of shaping the material does not require an additional step of dispersing the particles within the matrix with respect to the shaping method conventionally used for matrices without inclusion of particles.
• the shaping method can preferably be implemented on the equipment and processing lines conventionally used for matrices without inclusion of particles.
• the dispersion of the particles within the matrix may, in some embodiments, be carried out without additional chemical dispersing agent.
• the dispersion of the particles within the matrix is carried out in the presence of a chemical dispersing agent such as a surfactant.
• a chemical dispersing agent such as a surfactant.
• the dispersing agent may be used in an amount of 0.1 to 50% by weight relative to the mass of particles, especially in an amount of 0.5 to 20% by weight relative to the mass of particles .
• the particles according to the invention have the particularity of being dispersed substantially homogeneously in volume in the matrix, whatever their chemical nature, their morphology and the nature of the matrix. This means that the particle density per unit volume is the same at every point of the matrix.
• the density of particles per unit area is preferably about the same regardless of the surface of the matrix considered, whether it is an end surface of the matrix, or a "core" surface obtained by cutting the material for example.
• the anticorrosion property imparted to the matrix by inclusion of the particles according to the invention is distributed substantially homogeneously throughout the matrix volume.
• the material according to the invention may comprise particles according to the invention in any proportion adapted to give it the desired properties.
• the material can comprise from 0.1 to 80% by weight of particles relative to the total mass of matrix + particles, preferably from 1 to 60% by weight, in particular from 2 to 25% by weight.
• the particles according to the invention are non-deformable individualized particles.
• the surface of each particle that is in contact with other particles is very small.
• the radius of curvature of the meniscus forming the contact between two different particles of the assembly is less than 5%, preferably less than 2%, of the radius of each of the two particles, in particular within a matrix or in powder form.
• the sphericity of the particles according to the invention also makes it possible, for the same charge rate in a liquid matrix, to obtain a lower viscosity than with nonspherical particles.
• the particles according to the invention can be obtained by a process comprising non-dissociable and continuous stages in the same nebulization-heating reactor, the step of charging (or of incorporating) anticorrosion agents and of preparing the particles being carried out simultaneously. , in particular carried out at the nebulization stage.
• the method according to the invention makes it possible to obtain spherical, micronic, mesostructured particles loaded with anti-corrosion agents, the formation of the particles (and in particular their mesostructuration) and the incorporation of anticorrosion agents being concomitant.
• Another object of the present invention is a method for preparing a set of particles according to the invention.
• the process according to the invention is a process known as "aerosol pyrolysis" (or pyrolysis spray) which is carried out at drying temperatures and not necessarily pyrolysis.
• This process is an improved process compared to the aerosol pyrolysis process described in particular in application FR 2 973 260. More specifically, the process according to the invention is generally carried out in a nebulization-heating reactor, as detailed. below.
• This process comprises the non-dissociable and continuous stages in the same reactor, as follows: (1) the nebulization in a reactor of a liquid solution containing one or more precursors of the three-dimensional network of the particles, at a given molar concentration in a solvent, so as to obtain a mist of droplets of solution, the liquid solution also comprises at least one anticorrosive agent and optionally at least one surfactant,
• the nebulizing step (1) is preferably carried out at a temperature of 10 to 40 ° C, and / or preferably for a duration less than or equal to 10 seconds, in particular less than or equal to 5 seconds.
• the liquid solution is generally in the form of an aqueous or hydroalcoholic solution or in the form of a colloidal sol. More specifically, the liquid solution of step (1) is introduced into a reactor by nebulization.
• the heating step (2) (drying) is preferably carried out at a temperature of 40 to 120 ° C, and / or preferably for a duration of less than or equal to 10 seconds, in particular between 1 and 10 seconds.
• the step (3) is preferably carried out at a temperature of 120 to 400 ° C, and / or preferably for a duration less than or equal to 30 seconds, in particular between 10 and 30 seconds.
• the optional step (4) densification can be performed in a wide range of temperatures, especially between 200 and 1000 ° C. This step is preferably carried out at a temperature of 400 to 1000 ° C when the particles that are to be prepared are at least partly in crystallized form.
• the densification temperature may be lower, for example it may be around 200 ° C. to 300 ° C., in particular for amorphous silica.
• the densification step is performed for a period of less than or equal to 30 seconds, in particular between 20 and 30 seconds.
• the recovery step (5) is preferably carried out at a temperature below 100 ° C, and / or preferably for a duration of less than or equal to 10 seconds, in particular less than or equal to 5 seconds.
• the step (5) for recovering the particles is preferably carried out by depositing the particles on a filter at the outlet of the reactor.
• the advantage of the process according to the invention is that it can be achieved in a relatively short time.
• the duration of the process according to the invention may for example be less than a few minutes (for example 2 or 3 minutes, or even a minute).
• the temperatures of each of the steps may be outside the range of temperatures provided above. Indeed, for the same particles, the temperature to be applied may depend on the speed at which the droplets, the drops and the particles circulate in the reactor. The more the droplets, the drops and then the particles circulate rapidly in the reactor, the less time they spend there and the higher the temperature must be high to obtain the same result.
• steps (2), (3) and optionally (4) are carried out in the same reactor.
• all the steps of the process are carried out in the same reactor.
• steps (2), (3), and optionally (4) are carried out at increasing temperatures.
• All the steps of the process, in particular steps (2), (3) and optionally (4), are carried out in continuity with one another.
• the temperature profile applied in the reactor is adapted according to the particles that it is desired to form so that these two or three steps take place one after the other.
• the temperature in the reactor is adjusted via at least one, preferably 2 or 3, heating elements whose temperatures can be set independently.
• the method according to the present invention preferably furthermore comprises between step (3), or possibly the step of densification of the particles (4) when it is used, and the step of recovering the particles (5).
• a step (4 ') of quenching the particles is preferably carried out by entering a gas, preferably air, cold over all or part of the circumference of the reactor.
• a gas is said to be cold in the present invention if it is at a temperature of between 15 and 50 ° C, preferably between 15 and 30 ° C.
• the gas entering the reactor is a different gas from the air.
• it may be a neutral gas (such as nitrogen or argon), a reducing gas (such as hydrogen or carbon monoxide), or any mixture of such gases.
• the method is preferably implemented in the absence of a flow of gas vectorizing the fog from the bottom of the reactor.
• the laminar flow making it possible to bring the material into the zone in which the temperature is lower is advantageously created solely by suction at the top of the reactor, producing a depression for example of the order of a few pascals or a few tens of pascals.
• Such an embodiment makes it possible to use a reactor without gas entry in its lower part, thus limiting process disturbances and losses, and thus optimizing the process efficiency and the size distribution of the particles obtained.
• the reactor in which the process is implemented also includes a gas inlet at the level where the mist is formed.
• the gas entering the reactor at this level is preferably air, in particular hot air, that is to say at a temperature of 80 to 200 ° C.
• the method according to the invention does not include any other heating step than those implemented inside the aerosol pyrolysis reactor.
• these may comprise any constituent that it is possible to densify, in particular to crystallize, even the metastable phases.
• the particular conditions used in the process make it possible to preserve compounds of which the degradation temperature is lower than the actual temperature applied, because the time spent at high temperature is very short.
• the term "high temperature” preferably denotes a temperature greater than 40 ° C.
• “Time spent at high temperature” generally refers to the time spent on the drying, pyrolysis and densification steps.
• the time spent at high temperature does not exceed 70 seconds, in particular it is between 30 and 70 seconds.
• quenching is characterized by a cooling rate greater than or equal to 100 ° C per second.
• the particles according to the invention comprise a type of oxide which requires a supply of energy to densify, in particular to crystallize.
• alumina zinc oxide, iron oxide, titanium dioxide (rutile), and rare earth oxides (lanthanides and / or yttrium).
• Such particles can not be obtained in the same way by the conventional methods used in the prior art, especially those which do not include a quenching step.
• Those skilled in the art are able to adjust the time and the temperature passed in each of the steps according to the compounds introduced in step (1).
• FIG. 10 shows an example of a reactor scheme for implementing the method according to the invention.
• the lower part (1) of the reactor comprises the liquid solution containing a precursor or precursors of the three-dimensional network at a given molar concentration in a solvent. This solution is nebulized at the intermediate portion (2), and the droplets rise by suction in the reactor. The entry of cold gas, in particular cold air, allows quenching of the particles.
• the upper part (3) of the reactor is also at a cold temperature (below 100 ° C., for example between 15 and 50 ° C.).
• the precursor or the precursors of the three-dimensional network of the particles may be or may be of any origin, it (they) is (are) introduced in step (1) of the process in the form of a liquid solution, in particular an aqueous or hydroalcoholic solution containing the metal ions (such as an organic or inorganic salt of the metal in question) or the precursor molecules (such as organosilanes) or in the form of a colloidal sol (such as a colloidal dispersion of nanoparticles of the metal or of oxide of metal considered).
• the precursor (s) of the three-dimensional network is or are chosen according to the particles that it is desired to form.
• this precursor is at least partly derived from plant or food waste, which represents biosources.
• examples of such precursors of inorganic material include sodium silicate from rice husks.
• the three-dimensional network of which the particles are composed is constituted at least in part by a metallic component, possibly an organic-inorganic hybrid.
• This component can be obtained by sol-gel from at least one metal molecular precursor comprising one or more hydrolyzable groups of formula (1), (2), (3) or (4), optionally in the presence of at least one amphiphilic surfactant (or particular texturizing agent) as defined above, the surfactant being preserved in the final material.
• hydrolyzable group is meant a group capable of reacting with water to give a group -OH, which will undergo itself a polycondensation.
• Said metal precursor (s) containing one or more hydrolyzable groups is chosen from an alkoxide or a metal halide, preferably a metal alkoxide, or an alkynylmetal, of formula (1), (2) , (3) or (4) below:
• M represents Al (III), Ce (III), Ce (IV), Si (IV), Zr (IV), the number in parentheses being the valency of the M atom;
• n 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, especially C 2 -C 4, such as vinyl, 1-propenyl, 2-propenyl and butenyl; alkynyl groups, especially C 2 -C 4, such as acetylenyl and propargyl; aryl groups, in particular C 10, such as phenyl and naphthyl; methacryl or methacryloxy (C1-10 alkyl) groups such as methacryloxypropyl; epoxyalkyl or epoxyalkoxyalkyl groups in which the alkyl group is linear, branched or cyclic, C1-10, and the alkoxy group has from 1 to 10 carbon atoms, such as glycidyl and glycidyloxy (C1-10 alkyl); C2-10 haloalkyl groups such
• L represents a monodentate or polydentate complexing ligand, preferably polydentate, for example a carboxylic acid, preferably a C 1 -C 18 carboxylic acid, such as acetic acid, a C 5-20 ⁇ -diketone, for example acetylacetone, a ⁇ -diketone, preferably a C5-20 ketoester, such as methyl acetoacetate, a C5-20 ⁇ -ketoamide preferably, such as an N-methylacetoacetamide, preferably a C3-20 a- or ⁇ -hydroxyacid, such as lactic acid or salicylic acid, an amino acid such as alanine, a polyamine such as diethylenetriamine (or DETA), or a phosphonic acid or a phosphonate;
• a monodentate or polydentate complexing ligand for example a carboxylic acid, preferably a C 1 -C 18 carboxylic acid, such as acetic acid, a C 5-20 ⁇
• m represents the hydroxylation number of ligand L; and R "represents a non-hydrolyzable function chosen from alkylene groups, preferably C 1 -C 12, for example methylene, ethylene, propylene, butylene, hexylene, octylene, decylene and dodecylene, and alkynylene groups, preferably C 2 -C 12, by acetylenylene (-C ⁇ C-), -C ⁇ CC ⁇ C-, and -C ⁇ C-CeFi4-C ⁇ C-; N, N-di (C2-10 -alkylene) amino groups such as ⁇ , ⁇ -diethyleneamino; bis [N, N-di (C 2 -C 10) alkylene] amino groups such as bis [N- (3-propylene) -N-methyleneamino]; C 2 -C 10 mercaptoalkylene such as mercaptopropylene; C 2 -C 10 alkylene
• organosilane types such as:
• M is different from Si for formula (2).
• organoalkoxysilane of formula (3) there may be mentioned in particular 3-aminopropyltrialkoxysilane (RO) 3Si - (CH 2 ) 3 -NH 2 , 3- (2-aminoethyl) aminopropyltrialkoxysilane (RO) 3Si (CH 2 ) 3-NH- (CH 2 ) 2 -NH 2, 3- (trialkoxysilyl) propyldiethylenetriamine (RO) 3Si- (CH 2 ) 3 -NH- (CH 2) 2 -NH- (CH 2 ) 2 -NH 2 ; S-chloropropyltrialkoxysilane (RO) 3Si- (CH 2 ) 3Cl, 3-mercaptopropyltrialkoxysilane (RO) 3Si- (CH 2 ) 3SH; organosilyl azoles of N- (3-trialkoxysilylpropyl) -4,5-dihydroimidazole type, R
• bis-alkoxysilane of formula (4) a bis [trialkoxysilyl] methane (RO) 3 Si-CH 2 -Si (OR) 3, a bis (trialkoxysilyl) ethane (RO) 3 Si (preferably CH 2 ) 2 -Si (OR) 3 , a bis- [trialkoxysilyl] octane (RO) 3 Si- (CH 2 ) 8 -Si (OR) 3 , a bis [trialkoxysilyl-propyl] amine (RO) 3Si ( CH 2 ) 3-NH- (CH 2 ) 3 -Si (OR) 3, a bis- [trialkoxysilylpropyl] ethylenediamine (RO) 3Si- (CH 2) 3 -NH- (CH 2 ) 2 -NH- (CH 2 ) 3-Si (OR) 3; bis- [trialkoxysilylpropyl] disulfide (RO) 3Si
• an organic-inorganic hybrid is understood to mean a network consisting of molecules corresponding to formulas (2), (3) or (4).
• one of the phases of which the particles are composed is constituted at least in part by an organic liquid crystal phase.
• One or more amphiphilic surfactant (s) may be used in the invention as precursors of the liquid-crystal phase.
• the surfactants that can be used are defined previously.
• the anticorrosive agents can be introduced into the liquid solution in step (1) either in dry form or in the form of a liquid solution.
• the anti-corrosion agents are nanoparticles
• they can be introduced into the liquid solution of step (1) in the form of an aqueous or hydroalcoholic suspension comprising nanoparticles or else in dry form to be dispersed in the liquid solution of the step ( 1) of the process according to the invention.
• the anticorrosive agents are salts, they can be introduced into the liquid solution of step (1) in dry form or in dissolved form in an aqueous or aqueous-alcoholic solution.
• the process according to the invention makes it possible to obtain particles having a high degree of purity. These particles do not necessarily require the implementation of subsequent processing steps, such as washing, heat treatment, milling, etc., prior to use.
• the components introduced and used in the reactor are converted, which is an important advantage because the process generates little waste.
• the rate of use of atoms is high and complies with the requirements of green chemistry.
• the process according to the invention may optionally comprise at least one stage of post-treatment of the particles. For example, it may be a washing step with a suitable solvent, a contacting step with reducing conditions, a step of heating the particles, and / or a coating step particles, in particular for "sealing" said particles.
• a post-treatment step by heating the particles may be necessary to optimize the properties of the particles such as their composition or their crystalline structure.
• a post-treatment step by heating the particles will generally be less necessary as the speed of the drops and particles in the reactor will be less.
• the method according to the invention makes it possible to precisely control the size of the particles at the output of the process. Indeed, there is a constant ratio, which is around 5, between the diameter of the drops of the mist used and the diameter of the particles at the end of the process when the concentrations of precursors are molar, which is usually the case.
• the person skilled in the art knows how to determine, according to the concentration of precursor, the ratio between these two diameters. For example, if the precursor concentration is decreased by a factor of 10, then the size of the particles obtained is reduced by a cubic root factor of 10, or about 3.
• the diameter of the drops may also be controlled in particular by the parameters the nebulization mode, for example the frequency of the piezoelectric elements used to form the fog.
• the process according to the invention also makes it possible to precisely control the pore size at the output of the process.
• the pore size is controlled by the choice of the precursor compounds of the solution, their concentrations, the pH and the presence of anticorrosive agents and the possible addition of a surfactant in the liquid solution of step (1).
• the surfactant can thus act as a mesostructuring agent.
• the liquid solution of step (1) also comprises at least one surfactant, as defined above.
• silica which is the preferred matrix for mesoporous materials
• the precursor will condense around the micelles of surfactants in an aqueous medium.
• the concentration of surfactant in the solution can vary to a large extent. To give an order of magnitude, and according to a particular mode, the concentration of surfactants is between 0.001 and 0.1 mole for 1 mole of precursor of the metal in question.
• Another subject of the invention is a set of particles capable of being prepared according to the process defined above.
• the particles thus prepared have the characteristics described above. This process makes it possible in particular to obtain individualized spherical particles. Preferably, it also allows that each particle is not constituted by the aggregation of several smaller particles. Preferably, the particles obtained by this method are individualized and non-deformable.
• a final subject of the invention is a method for preparing a material according to the invention, comprising contacting a matrix as defined above with at least one set of particles according to the invention. This process then preferably comprises a step of shaping the material as described above.
• the LASER granulometry measurements were carried out using a LASER Mastersizer 2000 granulometer (Malvern Instruments), on dispersions of the particles in the water.
• the surfactant loading rate given in% by mass, corresponding to the ratio of the mass of surfactant to the total mass (Eq SiO 2 + surfactant + anti-corrosion agent).
• the rate of charge of anti-corrosion agent given in % by weight, corresponding to the ratio of the mass of anti-corrosion agent to the total mass (Eq SiO 2 + surfactant + anti-corrosion agent)
• the feed rates are the mass ratios introduced into the precursor solution before step (1) of the process.
• Brij®C10 Polyethylene glycol hexadecyl ether, sold by Sigma-Aldrich * use of MTEOS / TEOS mixture to give a more hydrophobic character to the particles
• TEOS tetraethoxysilane
• MTEOS methyltriethoxysilane
• the silica / Brij / BTA precursor solution is nebulized by the pyrolysis spray method according to the invention in step (1).
• step (2) and (3) 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 silica / Brij / 8HQ precursor solution is nebulized by the pyrolysis spray method according to the invention in step (1).
• step (2) and (3) 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 in step (5) on the filter and optionally dried under air.
• 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 - SAXS) but also after a step of calcination in air at 550 ° C. for 8 hours.
• the silica / BTA precursor solution is nebulized by the pyrolysis spray method according to the invention in step (1).
• step (2) and (3) 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 anticorrosion agent.
• the particles are recovered directly in step (5) on the filter and optionally dried under air.

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• 2014
  • 2014-12-15 FR FR1462447A patent/FR3029801A1/fr not_active Withdrawn
• 2015
  • 2015-12-14 EP EP15823646.3A patent/EP3234029A1/de not_active Withdrawn
  • 2015-12-14 CN CN201580076093.9A patent/CN107645968A/zh active Pending
  • 2015-12-14 WO PCT/FR2015/053474 patent/WO2016097558A1/fr active Application Filing
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