WO2009129783A2 - Procédé pour protéger un métal contre la corrosion - Google Patents

Procédé pour protéger un métal contre la corrosion Download PDF

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Publication number
WO2009129783A2
WO2009129783A2 PCT/DE2009/000516 DE2009000516W WO2009129783A2 WO 2009129783 A2 WO2009129783 A2 WO 2009129783A2 DE 2009000516 W DE2009000516 W DE 2009000516W WO 2009129783 A2 WO2009129783 A2 WO 2009129783A2
Authority
WO
WIPO (PCT)
Prior art keywords
metal
corrosion
steel
coating material
mixtures
Prior art date
Application number
PCT/DE2009/000516
Other languages
German (de)
English (en)
Other versions
WO2009129783A3 (fr
WO2009129783A8 (fr
Inventor
Christine Breyer
Stefan Goedicke
Stefan Sepeur
Original Assignee
Nano-X Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nano-X Gmbh filed Critical Nano-X Gmbh
Publication of WO2009129783A2 publication Critical patent/WO2009129783A2/fr
Publication of WO2009129783A3 publication Critical patent/WO2009129783A3/fr
Publication of WO2009129783A8 publication Critical patent/WO2009129783A8/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/082—Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
    • 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
    • C09D5/03—Powdery paints
    • C09D5/033—Powdery paints characterised by the additives
    • C09D5/038—Anticorrosion agents
    • 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
    • C09D5/10—Anti-corrosive paints containing metal dust
    • 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
    • C09D5/18—Fireproof paints including high temperature resistant 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
    • 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
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances

Definitions

  • the invention relates to a method for protecting a metal from corrosion.
  • Another approach to protecting metals from corrosion is to apply metallic coatings to the metal, such as by electroplating chrome, nickel, brass, etc. This creates good corrosion-resistant materials that are also visually appealing. However, this corrosion protection has no high temperature resistance and the materials are also poor or not deformable.
  • metal can be protected from corrosion by zinc paints, zinc dust coatings, galvanic zinc, but the zinc coating is not hard and not high temperature resistant.
  • JP 62-103305 A describes the application of nickel and cobalt powder with an organic binder and the subsequent sintering thereof. According to EP 0 459 637 B1, it is known to bind metal particles with an organic polymer and then sinter them.
  • the object of the invention is therefore to provide a method for protecting a metal from corrosion, with the good ductility and high temperature resistance of the corrosion-protected metal can be achieved.
  • a coating material which a. low-melting metal pigments whose melting point is less than 1000 ° C, b. one or more alloying elements and c.
  • the coating material is subjected to a temperature treatment at temperatures above the softening point of the metal pigment used, whereby the metal pigments combine with the alloying constituent (s) to form a new alloy.
  • the formation of alloy results in a change in the melting point and in the boiling point of the metal pigment used, the aim being predominantly to increase the melting point and boiling point "in situ.”
  • the alloy can also be formed as a gradient in the edge region of the pigments used.
  • the metal is steel or iron.
  • the coating material is applied by wet-chemical method or powder coating on the metal.
  • the electrochemical potential of the layer is less noble than the electrochemical potential of the metal, resulting in cathodic corrosion protection.
  • aluminum is included as a low melting point metal in the layer.
  • Aluminum has a higher melting point and is less noble than zinc, but aluminum is not suitable as a sacrificial element for cathodic corrosion protection of steel. This is related to the passivation of aluminum, which leads to the fact that the reaction rate of the oxidation of aluminum is so severely limited already after the coating with a dense monomolecular oxide skin that a further reaction practically does not take place.
  • a suitable alloying element it is possible to produce layers in which the passivation is eliminated and thus have both the good high-temperature resistance known from aluminum layers on steel and active cathodic protection against corrosion.
  • the low-melting metal pigments are selected from the group consisting of zinc, tin, lead, aluminum, magnesium, calcium, strontium, barium, sodium, potassium, lithium, bismuth, indium, cerium, tellurium, silver, Brass, bronze, nickel silver, mercury or mixtures thereof.
  • Pigments are understood as meaning particles having a particle size of from 100 ⁇ m to 500 ⁇ m, in particular from 1 ⁇ m to 100 ⁇ m.
  • the invention further includes that the alloying elements salts or nanoparticles of refractory metals (which melt due to the nanoparticulate again at lower temperatures), such as copper, iron, beryllium, cobalt, nickel, chromium, niobium, vanadium, molybdenum, manganese, tantalum, Osmium, tungsten, titanium, zirconium, gold, platinum or mixtures thereof.
  • alloying elements salts or nanoparticles of refractory metals (which melt due to the nanoparticulate again at lower temperatures), such as copper, iron, beryllium, cobalt, nickel, chromium, niobium, vanadium, molybdenum, manganese, tantalum, Osmium, tungsten, titanium, zirconium, gold, platinum or mixtures thereof.
  • the alloying elements During the softening of the low-melting metal pigments, the alloying elements increasingly diffuse deep into their surface with increasing temperature and lead to alloy formation starting at the surface of the particles up to complete penetration of the particles with sufficient treatment temperature and time.
  • the resulting alloys are composed of the corresponding high and low melting alloy components.
  • the compositions of some of the emerging alloys fall under the well-known names bronze, brass, hydronalium, titanium zinc, nickel silver, Tombak, etc., others are previously known under no name designation.
  • the binder comprises organic-inorganic compounds, in particular oligo- and polysiloxanes, from hydrolysis and condensation of alkylalkoxysilanes or alkoxysilanes or mixtures thereof, silicones or silicone resins, organically modified silicone resins or inorganic compounds, in particular silicates, polyphosphates, aluminosilicates, Metals, metal alkoxides and their condensation products; Contains or consists of metal oxides or metal salts.
  • the present invention is thus characterized in that no purely organic binders are used as in the prior art, but inorganic binders. It is not necessary to burn out the binder completely. Likewise, there is no sintering process after the expulsion of the binder.
  • the process of the present invention can be used to produce high temperature resistant anticorrosion coatings in the field of protection against scaling and corrosion of semi-finished products such as steel billets, billets, wires and tapes during and after manufacture and processing, anti-scaling in sheet and bulk warm and warm forging, e.g. Tempering or forging, the scale and corrosion protection of steel parts and semi-finished products during and after the tempering, e.g. Air, oil and water curing can be used.
  • semi-finished products such as steel billets, billets, wires and tapes during and after manufacture and processing
  • anti-scaling in sheet and bulk warm and warm forging e.g. Tempering or forging
  • the scale and corrosion protection of steel parts and semi-finished products during and after the tempering e.g. Air, oil and water curing can be used.
  • Zinkflake AT for example standard Zinkflake AT, from Eckart
  • 100 g of zinc particles are made up with 300 g of 20% strength copper (H) nitrate solution in l% aqueous sulfuric acid while stirring uniformly.
  • the addition of the copper (II) nitrate solution takes place slowly and in portions due to the strong heat of reaction.
  • the uniform stirring ensures that the entire zinc surface is evenly covered by copper. It is stirred for another 30 min. Thereafter, the supernatant solution is decanted off and the metal powder is dried in a circulating air oven at 100 ° C. for approx.
  • tetrabutyl orthotitanate 100 g are added with stirring to the dried metal particles and stirring is continued until a homogeneous particle distribution is achieved.
  • dilute with a suitable organic solvent e.g., ethanol.
  • the mixture is applied by means of a compressed air spray gun in the wet film on a steel sheet and baked for 10 min at 250 ° C as a layer.
  • the metal particles are transformed into an alloy of zinc and copper, which is also reflected in a brass-like hue of the layer after cooling to room temperature.
  • the metallic hybrid layer provides corrosion protection for the coated steel sheet.
  • the coating solution is applied by means of a Drucklufit spray gun in a wet film on a steel plate and baked for 10 min at 25O 0 C as a layer.
  • the metal particles are transformed into an aluminum-nickel alloy, which by Burning out the organic constituents of the silicone resin remaining SiO 2 matrix is attached to the steel substrate.
  • the hybrid layer formed provides corrosion protection for the coated steel sheet.
  • aluminum paste for example Stapa Metallux 2000, Eckart
  • 50 g of 1-butanol and homogeneously dispersed after addition of 150 g of tetrabutyl orthotitanate 100 g of aluminum paste (for example Stapa Metallux 2000, Eckart) are pasted with 50 g of 1-butanol and homogeneously dispersed after addition of 150 g of tetrabutyl orthotitanate.
  • 10 g of tetra-n-tin-butylate with stirring.
  • the aluminum pigments are held in suspension by continuous gentle stirring and applied to a steel tube with a brush in a covering layer.
  • the layer is dried for about 2 h at room temperature.
  • the coated steel tube is heated in an induction furnace under nitrogen atmosphere to about 800 ° C, held for 5 min at 800 ° C and then cooled back to room temperature.
  • the resulting metal-non-metal hybrid layer contains particles of an aluminum-tin alloy and protects the steel pipe from corrosion up to temperatures of> 500 ° C.

Abstract

L'invention concerne un procédé pour protéger un métal contre la corrosion. L'objectif de l'invention est de fournir un tel procédé permettant d'obtenir une bonne capacité de déformation et une haute résistance thermique du métal protégé contre la corrosion. À cet effet, le procédé selon l'invention consiste à appliquer sur le métal une matière de revêtement contenant a) des pigments métalliques à bas point de fusion, ce point de fusion étant inférieur à 1000°C, b) un ou plusieurs éléments d'alliage et c) des liants contenant des composés organo-inorganiques, en particulier des oligosiloxanes et des polysiloxanes, obtenus par hydrolyse et condensation d'alkylalcoxysilanes ou alcoxysilanes ou de mélanges de ceux-ci, des silicones ou des résines de silicones, des résines de silicones organiquement modifiées ou des composés inorganiques, en particulier des silicates, des polyphosphates, des aluminosilicates, des métaux, des alcoxydes métalliques et leurs produits de condensation; des oxydes métalliques ou des sels métalliques. Ce procédé consiste en outre à soumettre la matière de revêtement à un traitement thermique à des températures supérieures au point de ramollissement du pigment métallique utilisé, les pigments métalliques se combinant au ou aux composants d'alliage pour former un nouvel alliage. Dans le procédé selon l'invention, la formation de l'alliage entraîne une modification du point de fusion et du point d'ébullition du pigment métallique utilisé, une augmentation du point de fusion et du point d'ébullition "in situ" étant principalement recherchée. L'alliage peut également être réalisé sous forme de gradient dans la zone périphérique des pigments utilisés.
PCT/DE2009/000516 2008-04-22 2009-04-21 Procédé pour protéger un métal contre la corrosion WO2009129783A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008020216A DE102008020216B4 (de) 2008-04-22 2008-04-22 Verfahren zum Schützen eines Metalls vor Korrosion und Verwendung des Verfahrens
DE102008020216.9 2008-04-22

Publications (3)

Publication Number Publication Date
WO2009129783A2 true WO2009129783A2 (fr) 2009-10-29
WO2009129783A3 WO2009129783A3 (fr) 2010-04-15
WO2009129783A8 WO2009129783A8 (fr) 2010-12-29

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Country Status (2)

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DE (1) DE102008020216B4 (fr)
WO (1) WO2009129783A2 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010043220A1 (fr) * 2008-10-16 2010-04-22 Nano-X Gmbh Procédé permettant de constituer des couches anticorrosion déformables sur des surfaces métalliques
DE102011082835A1 (de) 2011-09-16 2013-03-21 Siemens Aktiengesellschaft Schichtmaterial zum Korrosionsschutz und Solarreceiver mit einem solchen Schichtmaterial
US9045829B2 (en) 2010-03-17 2015-06-02 Bilstein Gmbh & Co. Kg Process for producing a coated metal strip
KR20150096506A (ko) * 2012-12-17 2015-08-24 헨켈 아게 운트 코. 카게아아 열간 성형전에 강의 코팅을 위한 멀티-스테이지 방법
CN112076967A (zh) * 2020-09-18 2020-12-15 中煤科工开采研究院有限公司 一种环保型的钢板表面耐蚀处理技术
US20220195136A1 (en) * 2020-12-17 2022-06-23 Mazda Motor Corporation Addition-curing silicone resin for producing heat-shielding film, method for forming heat-shielding film on inner surface of combustion chamber of engine by means of addition-curing silicone resin, heat-shielding film, and heat shielding method for reducing or preventing heat dissipation from combustion chamber of engine to outside by means of heat-shielding film

Families Citing this family (3)

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Publication number Priority date Publication date Assignee Title
DE102012107633A1 (de) 2012-08-20 2014-02-20 Eckart Gmbh Zinkmagnesiumlegierung-Korrosionsschutzpigmente, Korrosionsschutzlack und Verfahren zur Herstellung der Korrosionsschutzpigmente
DE102013001498A1 (de) 2013-01-29 2014-07-31 NANO - X GmbH Lackaufbau und dessen Verwendung als Fahrzeuglack, Schiffslack, Bautenschutz- oder Industrielack
JP7120697B1 (ja) 2022-04-19 2022-08-17 嶋田金属株式会社 海洋生物の付着防止可能な構造物

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WO2006040030A1 (fr) * 2004-10-08 2006-04-20 Volkswagen Aktiengesellschaft Procede de revetement de surfaces metalliques
WO2007076766A2 (fr) * 2005-12-12 2007-07-12 Nano-X Gmbh Materiau de revetement destine a la protection de metaux, notamment d'acier, contre la corrosion et/ou l'oxydation, procede de revetement de metaux et element metallique
WO2008029833A1 (fr) * 2006-09-06 2008-03-13 Tsubakimoto Chain Co. Pigment antirouille à base d'eau, peinture antirouille à base d'eau et chaîne traitée en surface hautement anticorrosive
WO2009021489A2 (fr) * 2007-08-13 2009-02-19 Nano-X Gmbh Procédé de fabrication d'un revêtement actif, cathodique, anticorrosion sur des composants en acier

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Publication number Priority date Publication date Assignee Title
US20020017164A1 (en) * 2000-08-02 2002-02-14 Yasuhiko Endo Surface coated aluminum fine powder and aqueous chromium-free corrosion inhibiting coating composition including the same
WO2006040030A1 (fr) * 2004-10-08 2006-04-20 Volkswagen Aktiengesellschaft Procede de revetement de surfaces metalliques
WO2007076766A2 (fr) * 2005-12-12 2007-07-12 Nano-X Gmbh Materiau de revetement destine a la protection de metaux, notamment d'acier, contre la corrosion et/ou l'oxydation, procede de revetement de metaux et element metallique
WO2008029833A1 (fr) * 2006-09-06 2008-03-13 Tsubakimoto Chain Co. Pigment antirouille à base d'eau, peinture antirouille à base d'eau et chaîne traitée en surface hautement anticorrosive
WO2009021489A2 (fr) * 2007-08-13 2009-02-19 Nano-X Gmbh Procédé de fabrication d'un revêtement actif, cathodique, anticorrosion sur des composants en acier

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010043220A1 (fr) * 2008-10-16 2010-04-22 Nano-X Gmbh Procédé permettant de constituer des couches anticorrosion déformables sur des surfaces métalliques
US9045829B2 (en) 2010-03-17 2015-06-02 Bilstein Gmbh & Co. Kg Process for producing a coated metal strip
DE102011082835A1 (de) 2011-09-16 2013-03-21 Siemens Aktiengesellschaft Schichtmaterial zum Korrosionsschutz und Solarreceiver mit einem solchen Schichtmaterial
WO2013037623A1 (fr) 2011-09-16 2013-03-21 Siemens Aktiengesellschaft Matériau stratifié pour la protection contre la corrosion et récepteur solaire comprenant un tel matériau stratifié
KR20150096506A (ko) * 2012-12-17 2015-08-24 헨켈 아게 운트 코. 카게아아 열간 성형전에 강의 코팅을 위한 멀티-스테이지 방법
CN104903412A (zh) * 2012-12-17 2015-09-09 汉高股份有限及两合公司 热成形之前涂布钢的多步方法
CN104903412B (zh) * 2012-12-17 2017-04-26 汉高股份有限及两合公司 热成形之前涂布钢的多步方法
KR102146594B1 (ko) 2012-12-17 2020-08-20 헨켈 아게 운트 코. 카게아아 열간 성형전에 강의 코팅을 위한 멀티-스테이지 방법
CN112076967A (zh) * 2020-09-18 2020-12-15 中煤科工开采研究院有限公司 一种环保型的钢板表面耐蚀处理技术
US20220195136A1 (en) * 2020-12-17 2022-06-23 Mazda Motor Corporation Addition-curing silicone resin for producing heat-shielding film, method for forming heat-shielding film on inner surface of combustion chamber of engine by means of addition-curing silicone resin, heat-shielding film, and heat shielding method for reducing or preventing heat dissipation from combustion chamber of engine to outside by means of heat-shielding film
US11708472B2 (en) * 2020-12-17 2023-07-25 Mazda Motor Corporation Addition-curing silicone resin for producing heat-shielding film, method for forming heat-shielding film on inner surface of combustion chamber of engine by means of addition-curing silicone resin, heat-shielding film, and heat shielding method for reducing or preventing heat dissipation from combustion chamber of engine to outside by means of heat-shielding film

Also Published As

Publication number Publication date
WO2009129783A3 (fr) 2010-04-15
DE102008020216B4 (de) 2013-10-10
DE102008020216A1 (de) 2009-10-29
WO2009129783A8 (fr) 2010-12-29

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