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    • 1. 发明专利
    • FR2906539B1
    • 2009-01-09
    • FR0608614
    • 2006-10-02
    • EADS CCR GROUPEMENT D INTERETEADS EUROP AERONAUTIC DEFENCEUNIV PARIS CURIECENTRE NAT RECH SCIENT
    • CAMPAZZI ELISALANCELLE BELTRAN EMMANUELLESANCHEZ CLEMENT
    • C23C2/04B05D5/00B82B1/00B82B3/00C23F11/08
    • Structure comprises a mesostructured layer prepared by sol-gel method from a metallic molecular precursor of alkoxide or metal halide, in the presence of an amphiphilic surfactant and a metallic substrate. Structure comprises a mesostructured layer prepared by sol-gel method from a metallic molecular precursor of alkoxide or metal halide of formulae MZ n (I), (R 1) xMZ n - x (II), (L(m)) xMZ n - m x (III) or (RO) n - 1M-(R 2)-M(OR) n - 1 (IV), in the presence of an amphiphilic surfactant and a metallic substrate. M : Al (III), Ce (III), Ce (IV), Zr (IV), Sn (IV), Nb (V), V (V), Ta (V), Hf (V) or a rare earth (the figure between bracket is valency of the atom (M)), preferably Al (III), Ce (III), Ce (IV), Zr (IV), Nb (V), Y (III), La (III) or Eu (III); n : valency of (M); x : 1-n- 1; Z : halo or -OR; R : 1-4C alkyl, preferably methyl or ethyl; R 1non-hydrolyzable group comprising 1-4C alkyl, 2-4C alkenyl, 2-4C alkynyl, 6-10C aryl, methacryl or methacryloxy(1-10C alkyl), epoxy-1-10C alkyl or epoxy-1-10C alkoxy-1-10C alkyl, 2-10C haloalkyl, 2-10C perhaloalkyl, 2-10C mercaptoalkyl, 2-10C aminoalkyl, (2-10C aminoalkyl)amino(2-10C alkyl), di(2-10C alkylene)triamino(2-10 alkyl) or imidazolyl(2-10C alkyl), preferably methyl, ethyl, propyl, butyl, vinyl, 1-propenyl, 2-propenyl, butenyl, acetylenyl, propargyl, phenyl, naphthyl, methacryl, methacryloxypropyl, glycidyl, glycidyloxy(1-10C alkyl), 3-chloropropyl, perfluoropropyl, mercaptopropyl, 3-aminopropyl, 3-[(2-aminoethyl)amino]propyl or 3-[diethylenetriamine]propyl; L : mono or polydenatate, preferably polydentate complexing ligand; m : hydroxylation index of the ligand L, preferably carboxylic acid, beta -diketone, beta -keto ester, alpha or beta -hydroxy acid, amino-acid, polyamine, phosphonic acid or phosphonate; and R 2non-hydrolyzable group comprising 1-12C alkylene, N,N-di(2-10C alkylene)amino, bis[N,N-di(2-10C alkylene)amino], 2-10C mercaptoalkylene, (2-10C alkylene)polysulfide, 2-4C alkenylene, 6-10C arylene, di(2-10C alkylene)-6-10C arylene or N,N'-di(2-10C alkylene)ureido, preferably methylene, ethylene, propylene, butylene, hexylene, octylene, decylene, dodecylene, N,N-diethyleneamino, di [N(3-propylene)-N-methyleneamino], mercaptopropylene, propylene-disulfide, propylenetetrasulfide, vinylene, phenylene, di(ethylene) phenylene or N,N'-dipropyleneureido. An independent claim is included for the preparation of the structure comprising preparation of a sol-gel material by hydrolysis-condensation of the metallic molecular precursors (I)-(IV) optionally in combination with a precursor based on silicon as silicon alkoxide, organoalkoxysilane or silicon halide i.e. (V)-(VIII), in aqueous or water/alcohol medium, in the presence of an amphiphilic surfactant and optionally a functionalizing agent, deposition of the obtained material on a metal substrate, treating the covered substrate, thermally, chemically and/or using UV treatment to densify the network, followed by washing, optionally eliminating the surfactant molecules by thermal treatment and/or chemical extraction and optionally functionalization.
    • 10. 发明专利
    • FR2914631B1
    • 2009-07-03
    • FR0754375
    • 2007-04-06
    • EADS EUROP AERONAUTIC DEFENCEUNIV PARIS 6 PIERRE ET MARIE CCENTRE NAT RECH SCIENT
    • CAMPAZZI ELISALANCELLE BELTRAN EMMANUELLESANCHEZ CLEMENT
    • B82B1/00B82B3/00C09D1/00C09D5/10C23C22/56
    • Nanostructured material (A) comprises at least an elementary nanoblock made of silica, alumina, zirconia, titanium oxide or cerium (IV), and functionalized with at least two functionalizing agents (I), (II), and (III). Nanostructured material (A) comprises at least an elementary nanoblock made of silica, alumina, zirconia, titanium oxide or cerium (IV), and functionalized with at least two functionalizing agents of formulae (Z 4-xSi((R1a) p-F1) x) (I), (Z 4-x-y(F1a-(R1a) p) ySi((R1a) p-F1) x) (II), and (Z n-ma-mb(F1a-L) maM(L-F1) mb) (III). Z : halo or -OR; R : 1-4C alkyl; x, y : 1-3; R1a : organic spacer group comprising 1-4C alkaline, 2-4C alkenylene, or 6-10C arylene; p : 0-1; F1 : 1-4C alkyl, 2-4C alkenyl, 2-4C alkynyl, 6-10C aryl, methacryl or methacryloxy(1-10C alkyl), epoxyalkyl or epoxyalkoxyalkyl (where the alkyl comprises 1-10C and alkoxy comprises 1-10C), 2-10C halo alkyl, 2-10C perhaloalkyl, 2-10C mercaptoalkyl, 2-10C aminoalkyl, amino(2-10C)amino(2-10C alkyl), di(2-10C alkylene)triamino(2-10C alkyl) or imidazolyl(2-10C alkyl); F1a, L : monodentate or polydentate ligand complex, preferably polydentate; M : Al(III), Ce(III), Ce(IV), Zr(IV), Ti(IV), Sn(IV), Nb(V), V(V), Ta(V), Hf(V), or a rare earth comprising Y(III), La(III) or Eu(III); n : state of coordination of atom (M); m : number of coordination bond between L and M; and a, b : integers of ma+mb= n. Provided that 4-x>= 1 for (I) and 4-x-y>= 0 for (II). Independent claims are included for: (1) a process of preparing (A), comprising: (a) preparing elementary nanoblocks by a hydrolytic or non-hydrolytic process from at least a metallic alkoxide or metal halide; (b)functionalizing the elementary nanoblocks using the functionalizing agent; (c) preparing an organic/inorganic hybrid matrix by sol-gel, from the metal alkoxide, where the preparation by sol-gel being in the presence of a solvent, and optionally a catalyst; and (d) mixing the functionalized elementary nanoblocks and the matrix; (2) an article comprising metal substrate and at least a surface consisting of at least (A); and (3) a process for preparing the article, comprising soaking (A) in a bath, and depositing on substrate by rotation, spraying, laminate coating or brush.