EP2737100B1 - Verfahren zur substratbeschichtung und verwendung additivversehener, pulverförmiger beschichtungsmaterialien in derartigen verfahren - Google Patents

Verfahren zur substratbeschichtung und verwendung additivversehener, pulverförmiger beschichtungsmaterialien in derartigen verfahren Download PDF

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Publication number
EP2737100B1
EP2737100B1 EP12741313.6A EP12741313A EP2737100B1 EP 2737100 B1 EP2737100 B1 EP 2737100B1 EP 12741313 A EP12741313 A EP 12741313A EP 2737100 B1 EP2737100 B1 EP 2737100B1
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EP
European Patent Office
Prior art keywords
coating material
additive
particles
spraying
thermal plasma
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EP12741313.6A
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German (de)
English (en)
French (fr)
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EP2737100A2 (de
Inventor
Sebastian HÖFENER
Markus RUPPRECHT
Christian Wolfrum
Marco Greb
Andreas Reis
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Eckart GmbH
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Eckart GmbH
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Priority claimed from DE102011052120A external-priority patent/DE102011052120A1/de
Priority claimed from DE102011052119A external-priority patent/DE102011052119A1/de
Application filed by Eckart GmbH filed Critical Eckart GmbH
Publication of EP2737100A2 publication Critical patent/EP2737100A2/de
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    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • 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
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/067—Metallic material containing free particles of non-metal elements, e.g. carbon, silicon, boron, phosphorus or arsenic
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/123—Spraying molten metal
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/129—Flame spraying
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134—Plasma spraying

Definitions

  • the present invention deals with the use of powdered coating materials for coating substrates. Further, the present invention includes methods of substrate coating using such powdery coating materials. Furthermore, the present invention comprises powdery coating materials which are suitable for the aforementioned uses and / or processes.
  • a variety of coating techniques have been developed to provide the desired properties for the particular application.
  • Known methods use for generating the coatings, for example, kinetic energy, thermal energy or mixtures thereof, wherein the thermal energy may for example come from a conventional combustion flame or a plasma flame.
  • the latter are further distinguished in thermal and non-thermal plasmas, which have in common that a gas has been partially or completely separated into free charge carriers such as ions or electrons.
  • the formation of the coating takes place by applying a powder to a substrate surface, the powder particles being greatly accelerated.
  • a heated process gas is accelerated by expansion in a Laval nozzle to supersonic speed and then injected the powder. Due to the high kinetic energy, the particles form a dense layer upon impact with the substrate surface.
  • the WO 2010/003396 A1 the use of cold gas spraying as a coating method for the application of wear protection coatings. Furthermore, there are revelations of the cold gas spraying process, for example in EP 1 363 811 A1 . EP 0 911 425 B1 and US 7,740,905 B2 ,
  • Flame spraying belongs to the group of thermal coating processes.
  • a powdery coating material is introduced into the flame of a fuel gas-oxygen mixture.
  • acetylene oxygen flames temperatures of up to about 3200 ° C. become. Details on the procedure may be publications such as EP 830 464 B1 and US 5,207,382 A be removed.
  • thermal plasma spraying a powdery coating material is injected into a thermal plasma.
  • temperatures of up to about 20,000 K are reached, whereby the injected powder melts and is deposited as a coating on a substrate.
  • thermal plasma spraying and specific embodiments as well as process parameters are known to the person skilled in the art. Exemplary will be on the WO 2004/016821 which describes the use of thermal plasma spraying to apply an amorphous coating. Further, for example, discloses EP 0 344 781 the use of flame spraying and thermal plasma spraying as a coating method using a tungsten carbide powder mixture. Specific devices for use in plasma spraying methods have been widely described in the literature, such as in US Pat EP 0 342 428 A2 . US 7,678,428 B2 . US 7,928,338 B2 and EP 1 287 898 A2 ,
  • the non-thermal plasma spraying is largely analogous to thermal plasma spraying and flame spraying.
  • a powder coating material is injected into a non-thermal plasma and applied to a substrate surface.
  • Such as the EP 1 675 971 B1 can be removed, this method is characterized by a particularly low thermal stress of the coated substrate.
  • This method, particular embodiments and corresponding process parameters are known to the skilled person from various publications. For example, this describes EP 2 104 750 A2 the application of this method and an apparatus for carrying it out. For example DE 103 20 379 A1 describes the production of an electrically heatable element using this method. Further disclosures regarding the method or devices for non-thermal plasma spraying can be found, for example, in US Pat EP 1 675 971 B1 .
  • a general problem of coating methods using a powdery coating material is the promotion of the powder.
  • a very uniform supply of the powdery coating material is necessary.
  • the EP 0 459 115 A1 relates to a thermal spray powder.
  • the object of the present invention is to enable the production of novel coatings or to improve the production of known coatings. Furthermore, it is an object of the present invention to enable the production of high-quality, particularly thin coatings. Further, it is an object of the present invention to solve existing problems regarding the conveyability of the powdery coating material used in a coating process.
  • Another object of the present invention is to provide a substrate coating process characterized by novel coatings or improved coating quality.
  • Another object of the present invention is to provide a powdery coating material which is particularly suitable for one of the aforementioned uses in coating processes.
  • the present invention relates to the use of a particle-containing powdery coating material according to claim 1.
  • the weight proportion of the additive (s) is at most 32% by weight, based on the total weight of the coating material and the additive.
  • the weight proportion of the additive or additives is between 0.02% and 32% by weight, each based on the total weight of the coating material and the additive.
  • the carbon content of the additive-coated particles of the powdery coating material is from 0.01% to 15% by weight, based on the total weight of the coating material and the additive.
  • the weight proportion of the additive or additives is at least 0.02% by weight, based on the total weight of the coating material and of the additive.
  • the compound used as an additive or have the compounds used as an additive at least 6 carbon atoms.
  • the particles of powdered coating material include or are metal particles and the metal is selected from the group consisting of silver, gold, platinum, palladium, vanadium, chromium, manganese, cobalt, germanium, antimony, aluminum, zinc, tin , Iron, copper, nickel, titanium, silicon, alloys and mixtures thereof.
  • the coating process is selected from the group consisting of. Flame spraying and non-thermal plasma spraying. Particularly preferred is non-thermal plasma spraying.
  • the at least one additive does not comprise stearic acid and / or oleic acid and preferably no saturated and unsaturated C 18 carboxylic acids, more preferably no saturated and unsaturated C 14 to C 18 carboxylic acids, even more preferably no saturated and unsaturated C 12 to C 18 carboxylic acids, and most preferably no saturated and unsaturated C 10 to C 20 carboxylic acids.
  • the additive or additives are selected from the group consisting of polymers, monomers, silanes, waxes, oxidized waxes, carboxylic acids, phosphonic acids, derivatives of the abovementioned and mixtures thereof.
  • the additive or additives are removable from the coated particles with organic and / or aqueous solvent.
  • the powdery coating material has a particle size distribution with a D 50 value in the range from 1.5 to 53 ⁇ m.
  • the powdery coating material has a particle size distribution with a D 90 value in the range of 9 to 103 ⁇ m.
  • the powdery coating material has a particle size distribution with a D 10 value in the range of 0.2 to 5 ⁇ m.
  • the present invention relates to methods for coating a substrate according to claim 10.
  • the method is selected from the group consisting of flame spraying and non-thermal plasma spraying.
  • the method is non-thermal plasma spraying.
  • the powdery coating material is conveyed as an aerosol.
  • the medium directed to the substrate is air or was generated from air.
  • the aforementioned air can be taken from the ambient atmosphere.
  • the air is cleaned prior to its use, wherein, for example, dust and / or water vapor is separated.
  • the gaseous constituents of the air are substantially completely separated apart from nitrogen and oxygen, the total amount of the impurities preferably being ⁇ 0.01% by volume, more preferably ⁇ 0.001% by volume.
  • powder coating material in the context of the present invention refers to a particle mixture which is applied to the substrate as a coating.
  • the provision of the surface of the particles of the powdery coating material with the additive or the additives need not be complete in this case in order to enable the use according to the invention. Without intending to be construed as limiting the invention, it is the view of the inventors that the effect of the applied additives is inter alia caused by an effect as a spacer between the individual particles, wherein a deposition or coverage of the surface over a certain degree
  • conveyability with no noticeably improved conveyability is connected, but requires an increased use of the additive or additives, which therefore causes only costs and therefore does not make economic sense.
  • At most 90%, preferably at most 85%, more preferably at most 80%, even more preferably at most 75%, and most preferably at most 70% of the surface area of the particles be coated with the additive (s) .
  • the fullest possible occupation of the surface of the particles offers a certain protective effect, for example against oxidizing influences from the environment.
  • at least 20%, preferably at least 25%, more preferably at least 30%, and even more preferably at least 35% of the surface area of the particles be coated with the additive (s).
  • At least 40%, preferably at least 50%, more preferably at least 55% and even more preferably at least 60% of the surface area of the particles are coated with the additive (s).
  • a determination of the surface coverage of the powdery coating materials according to the invention is carried out by means of SEM, whereby 30 randomly selected particles are considered.
  • the inventors have found that the conveyability of a powdery coating material is significantly increased by the at least partial coverage of the surface of the particles with at least one additive. This is of great importance in coating processes, in particular those in which a thin layer is to be applied, in order to obtain high-quality and reproducible results.
  • An increase in the reproducibility of the process and more uniform delivery of the powdery coating material also allows the production of much more homogeneous coatings with little defects and a very high degree of crosslinking of the particles.
  • Such features are of particular importance for the production of particularly thin coatings.
  • such improved conveyability results in a significantly simplified supply of the powdered coating material and a drastic reduction in the expenditure on equipment.
  • Inventive methods used to build coatings include cold gas spraying, thermal plasma spraying, non-thermal plasma spraying, flame spraying, and high velocity flame spraying. Of particular importance is improved conveyability, especially in coating processes in which the lowest possible thermal load on the substrate is to be produced and no or almost no thermal component is used for the application of the coating. In certain embodiments, therefore, the use of the powdery coating material according to the invention in flame spraying, non-thermal plasma spraying, cold gas spraying and high-speed flame spraying is preferred. In certain cases, it is also desirable to be able to coat even sensitive substrates with the method according to the invention, which is why the powdery coating material may be applied with only limited kinetic energy.
  • the method is therefore preferably selected from the group consisting of flame spraying and non-thermal plasma spraying.
  • flame spraying requires the use and to ensure continuous operation, the storage of large quantities of the gas used. Since flammable gases require flammable gases to produce the flame, their storage is associated with a corresponding safety risk and therefore requires special safety regulations.
  • a plasma can also be generated using non-combustible gases, so that the storage of corresponding amounts of gas is associated with lower safety standards and therefore reduced costs.
  • the non-thermal plasma spraying is used as a coating method.
  • additive in the context of the present invention refers to substances which are uncrosslinked on the surface of the particles of the powdery coating material, ie were not crosslinked.
  • additive refers to carbonaceous compound that has not been crosslinked on the surface of the particles of powdered coating material.
  • not crosslinked on the surface is understood to mean that no covalent bonds are formed between the individual additive molecules during or after the application of the additive to the particles of the powdered coating material, thus no postcrosslinking takes place on the pigment surface.
  • additive does not mean crosslinked polymers, as described, for example, in US Pat EP 2115075 A1 be revealed.
  • the additives are applied to the particles of the powdered material only by means of physical bonds Coating material are bound, for example by means of Van der Waals interactions, dipole interactions or hydrogen bonds. However, it is also possible that the additives are additionally or alternatively bound by means of chemical bonds such as covalent or ionic bonds to the surface of the particles of the powdery coating material.
  • the additives according to the invention can be removed again from the particles by the use of organic and / or aqueous solvents.
  • Such additives have the particular advantage that they are easy and inexpensive to apply.
  • certain preferred additives may, for example, be dispersed in a solvent and applied to the powder particles by mechanical forces. Additionally or alternatively, in certain embodiments, the additives may be dissolved in a suitable solvent, then mixed with the powder particles and applied to the powder particles by evaporation of the solvent.
  • Substances which are additives for the purposes of the present invention are in particular carbon-containing compounds which are bound chemically and / or physically to the surface of the particles of the powdery coating material.
  • the weight fraction of the carbon atoms of the additive-containing powdery coating material is at least 0.01% by weight, preferably at least 0.05% by weight, more preferably at least 0.1% by weight, and even more preferably at least 0.17 wt .-% is.
  • the weight fraction of carbon atoms of the additive-coated powdery coating material be at least 0.22 wt%, preferably at least 0.28 wt%, more preferably at least 0.34 wt%, and even more preferably at least 0.4 wt .-% is.
  • the aforementioned% by weight refers to the total weight of the coating material and the additive.
  • the weight ratio of the carbon atoms of the additive-containing powdery coating material is at most 15% by weight, preferably at most 10% by weight, more preferably at most 7% by weight, and still more preferably at most 5% by weight. is.
  • the carbon content is at most 4 wt%, preferably at most 3 wt%, more preferably at most 2 wt%, and even more preferably at most 1 wt%.
  • the aforementioned% by weight refers to the total weight of the coating material and the additive.
  • the weight fraction of the carbon atoms of the additive-containing powdery coating material in the range between 0.01 wt .-% and 15 wt .-%, preferably in the range between 0.05 wt .-% and 10 wt. %, more preferred in the range between 0.1 wt .-% and 7 wt .-% and even more preferably in the range between 0.17 wt .-% and 5 wt .-%.
  • the weight fraction of the carbon atoms of the additive-containing powdery coating material in the range between 0.22 wt .-% and 4 wt .-%, preferably in the range between 0.28 wt .-% and 3 wt %, more preferably in the range between 0.34 wt .-% and 2 wt .-% and even more preferably in the range between 0.4 wt .-% and 1 wt .-% is.
  • the aforementioned% by weight refers to the total weight of the coating material and the additive.
  • the determination of the weight fraction of the carbon atoms in the total weight of the coating material and of the additive takes place, for example, with a CS 200 device from Leco Instruments GmbH.
  • the compounds employed as the additive contain at least 6 carbon atoms, preferably at least 7 carbon atoms, more preferably at least 8 carbon atoms and even more preferably at least 9 carbon atoms.
  • the compounds employed as the additive contain at least 10 carbon atoms, preferably at least 11 carbon atoms, more preferably at least 12 carbon atoms and even more preferably at least 13 carbon atoms.
  • the number of carbon atoms contained in the additive according to the invention can be determined, for example, by determining the particular additive. In this case, all methods known to the person skilled in the art for determining a substance can be used.
  • an additive using organic and / or aqueous solvents can be detached from the particles of the powdered coating material and subsequently identified by means of HPLC, GCMS, NMR, CHN or combinations of the abovementioned with one another or with other routinely used methods.
  • the weight proportion of the additive (s) is at least 0.02 wt.%, Preferably at least 0.08 wt.%, More preferably at least 0.17 wt.%, And even more preferably at least 0.30 wt .-% is.
  • the C content of the coating material and the additive be at least 0.35 wt.%, Preferably at least 0.42 wt.%, More preferably at least 0.54 wt even more preferably at least 0.62 wt .-% is.
  • the aforementioned% by weight refers to the total weight of the coating material and the additive.
  • the weight fraction of the additive is at most 32% by weight, preferably at most 18% by weight, more preferably at most 13% by weight and even more preferably at most 9% by weight.
  • the C content of the coating material and the additive is at most 7% by weight, preferably at most 6% by weight, more preferably at most 4.5% by weight, and still more preferably at most 2.3 wt .-% is.
  • the aforementioned% by weight refers to the total weight of the coating material and the additive.
  • the weight proportion of the additive ranges between 0.02 wt% and 32 wt%, preferably between 0.08 wt% and 18 wt%, more preferably in the range between 0.17 wt .-% and 13 wt .-% and even more preferably in the range between 0.30 wt .-% and 9 wt .-% is.
  • the weight fraction of the carbon atoms of the coating material and the additive ranges between 0.35 wt.% And 7 wt.%, Preferably Range between 0.42 wt% and 6 wt%, more preferably between 0.54 wt% and 4.5 wt% and even more preferably in the range between 0.62 wt% and 2.3 wt .-% is.
  • the aforementioned% by weight refers to the total weight of the coating material and the additive.
  • Substances which are used as additives for the purposes of the present invention are: Polymers (eg polysaccharides, plastics), monomers, silanes, waxes, oxidized waxes, carboxylic acids (eg fatty acids), phosphonic acids, derivatives of the aforementioned (in particular carboxylic acid derivatives and phosphoric acid derivatives) and mixtures thereof.
  • polysaccharides, plastics, silanes, waxes, oxidized waxes, carboxylic acids (eg fatty acids), carboxylic acid derivatives, phosphonic acids, phosphoric acid derivatives or mixtures thereof preferably polysaccharides, silanes, waxes, oxidized waxes, carboxylic acids (eg fatty acids), carboxylic acid derivatives, Phosphonic acids, phosphoric acid derivatives or mixtures thereof, more preferably polysaccharides, silanes, waxes, oxidized waxes, phosphonic acids, phosphoric acid derivatives or mixtures thereof, can be used as an additive.
  • the aforementioned waxes include natural waxes as well as synthetic waxes.
  • waxes are paraffin waxes, petroleum waxes, montan waxes, animal waxes (eg beeswax, shellack, wool wax), vegetable waxes (eg carnauba wax, candelilla wax, rice wax), fatty acid amide waxes (such as erucamide), polyolefin waxes (such as polyethylene waxes, polypropylene waxes), grafted polyolefin waxes , Fischer-Tropsch waxes, and oxidized polyethylene waxes and modified polyethylene and polypropylene waxes (eg metallocene waxes).
  • the waxes of the invention are preferably bonded via physical bonds in certain embodiments. However, it is not excluded that the waxes are added further specific embodiments have functional groups which allow alternatively or additionally an ionic and / or covalent bond.
  • polymer in the context of the present invention also encompasses oligomers.
  • the polymers used in this invention are preferably composed of at least 25 monomer units, more preferably at least 35 monomer units, even more preferably at least 45 monomer units, and most preferably at least 50 monomer units.
  • the polymers may in this case be bound to the particles of the powdery coating material without covalent or ionic bonding being formed.
  • the additive of the invention can form at least one ionic or covalent bond to the particles of the powdered coating material. Such bonding preferably takes place in certain of the abovementioned embodiments via a phosphoric acid, carboxylic acid, silane or sulfonic acid group contained in the polymer.
  • polysaccharide within the meaning of the present invention also includes oligosaccharides.
  • the polysaccharides used in the invention are preferably composed of at least 4 monomer units, more preferably at least 8 monomer units, even more preferably at least 10 monomer units, and most preferably at least 12 monomer units.
  • Particularly preferred polysaccharides in certain embodiments are cellulose, cellulose derivatives such as methylcellulose, ethylcellulose, carboxymethylcelluose, hydroxyethylcellulose, hydroxypropylmethylcellulose, nitrocellulose (eg, Ethocel or Methocel from Dow Wolff cellulosics), cellulose esters (eg, cellulose acetate, cellulose acetobutyrate, and cellulose propionate), such as starch Corn starch, potato starch and wheat starch and modified starches.
  • cellulose cellulose derivatives such as methylcellulose, ethylcellulose, carboxymethylcelluose, hydroxyethylcellulose, hydroxypropylmethylcellulose, nitrocellulose (eg, Ethocel or Methocel from Dow Wolff cellulosics), cellulose esters (eg, cellulose acetate, cellulose acetobutyrate, and cellulose propionate), such as starch Corn starch, potato starch and wheat starch and
  • plastic in the sense of the present invention encompasses thermoplastic, thermosetting or elastomeric plastics, thermoplastic materials being particularly preferred, all thermoplastics known to those skilled in the art being suitable Plastic Paperback, ed. Saechtling, 25th edition, Hanser-Verlag, Kunststoff, 1992 , in particular chapter 4 and references cited therein, and in Kunststoff-Handbuch, ed. G. Becker and D.
  • thermoplastics are to be exemplified for clarification: polyoxyalkylenes, polycarbonates (PC), polyesters such as polybutylene terephthalate (PBT) or polyethylene terephthalate (PET), polyolefins such as polyethylene or polypropylene (PP), poly (meth) acrylates, Polyamides, vinylaromatic (co) polymers such as polystyrene, impact-modified polystyrene such as HI-PS, or ASA, ABS or AES polymers, polyarylene ethers such as polyphenylene ether (PPE), polysulfones, polyurethanes, polylactides, halogen-containing polymers, imid weakness audience polymers, cellulose esters, silicone Polymers and thermoplastic elastomers. It is also possible to use mixtures of different thermoplastics in the form of single- or multi-phase polymer blend
  • Polyoxyalkylene homopolymers or copolymers in particular (co) polyoxymethylenes (POM), and processes for their preparation are known per se to the person skilled in the art and are described in the literature.
  • the polymer backbone of these polymers has at least 50 mole% of repeating units -CH 2 O-.
  • the homopolymers are generally prepared by polymerization of formaldehyde or trioxane, preferably catalytically. Examples are polyoxymethylene copolymers and Polyoxymethylenterpolymerisate.
  • Suitable polycarbonates are known per se and are, for example, according to DE 1 300 266 B1 by interfacial polycondensation or according to DE 14 95 730 A1 by reaction of biphenyl carbonate with bisphenols available.
  • polyesters are also known per se and described in the literature.
  • the polyesters can be prepared by reacting aromatic dicarboxylic acids, their esters or other ester-forming derivatives thereof with aliphatic dihydroxy compounds in a manner known per se.
  • the dicarboxylic acids used are naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid or mixtures thereof.
  • Up to 10 mol% of the aromatic dicarboxylic acids can be replaced by aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids.
  • aliphatic dihydroxy compounds are diols having 2 to 6 carbon atoms, in particular 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,4-cyclohexanediol and neopentyl glycol or mixtures thereof.
  • polyolefins examples include polyethylene and polypropylene and copolymers based on ethylene or propylene, optionally also with higher ⁇ -olefins.
  • polyolefin in the sense of the present invention also encompasses ethylene-propylene elastomers and ethylene-propylene terpolymers.
  • poly (meth) acrylates examples are polymethyl methacrylate (PMMA) and copolymers based on methyl methacrylate with up to 40% by weight of further copolymerizable monomers, e.g. n-butyl acrylate, t-butyl acrylate or 2-ethylhexyl acrylate.
  • PMMA polymethyl methacrylate
  • copolymers based on methyl methacrylate with up to 40% by weight of further copolymerizable monomers, e.g. n-butyl acrylate, t-butyl acrylate or 2-ethylhexyl acrylate.
  • the aforementioned polyamides also include polyetheramides such as polyether block amides and are described, for example, in the disclosures of US 2,071,250 . US 2,071,251 . US 2,130,523 . US 2,130,948 . US 2,241,322 . US 2,312,966 . US 2,512,606 and US 3,393,210 described.
  • the aforementioned polyamides include, for example, polycaprolactams, polycapryllactams, polylaurolactams, and polyamides obtained by reacting dicarboxylic acids with diamines. Examples of suitable dicarboxylic acids are alkanedicarboxylic acids having 6 to 12, in particular 6 to 10 carbon atoms and aromatic dicarboxylic acids used.
  • suitable diamines are alkanediamines having 6 to 12, in particular 6 to 8 carbon atoms, and m-xylylenediamine, di (4-aminophenyl) methane, di (4-aminocyclohexyl) methane, 2,2-di- (4-aminophenyl) propane or 2,2-di (4-aminocyclohexyl) propane.
  • SAN styrene-acrylonitrile copolymers
  • HIPS impact-modified polystyrene
  • ASA acrylonitrile-styrene-acrylic ester
  • ABS acrylonitrile-butadiene-styrene
  • AES acrylonitrile-EPDM-rubber-styrene).
  • ABS polymers can be found, for example, in DE 197 28 629 A1 and of ASA polymers, for example in EP 99 532 A2 .
  • Information about the production of AES polymers can also be found for example in the US 3,055,859 or in the US 4,224,419 ,
  • polyarylene ethers examples include polyarylene ethers per se, polyarylene ether sulfides, polyarylene ether sulfones and polyarylene ether ketones.
  • Their arylene groups may be identical or different and independently of one another, for example, an aromatic radical having 6 to 18 carbon atoms.
  • suitable arylene radicals are phenylene, bisphenylene, terphenylene, 1,5-naphthylene, 1,6-naphthylene, 1,5-anthrylene, 9,10-anthrylene or 2,6-anthrylene.
  • Exemplary preparation data of polyarylene ether sulfones can be found in EP 113 112 A1 and EP 135 130 A2 ,
  • polymers of lactic acid, polylactides, and processes for their preparation are known in the art. In certain embodiments, it is particularly preferred to use copolymers or block copolymers based on lactic acid and other monomers.
  • halogen-containing polymers are the polymers of vinyl chloride, such as polyvinyl chloride (PVC) (e.g., rigid PVC and plasticized PVC), and copolymers of vinyl chloride (e.g., PVC-U molding compounds).
  • PVC polyvinyl chloride
  • PVC-U molding compounds copolymers of vinyl chloride
  • PTFE polytetrafluoroethylene
  • FEP tetrafluoroethylene-perfluoropropylene copolymers
  • EFE tetrafluoroethylene-perfluoropropylene copolymers
  • ETDFE ethylene-tetrafluoroethylene copolymers
  • PVDF polyvinylidene fluoride
  • imide group-containing polymers examples include polyimides, polyetherimides, and polyamide-imides. Such polymers are for example in Römpp Chemie Lexikon, CD-ROM Version 1.0, Thieme Verlag Stuttgart 1995 , described.
  • thermoplastic elastomers are characterized in that they can be processed like thermoplastics, but have elastomeric properties. Further information can be found for example in G. Holden et al., Thermoplastic Elastomers, 2nd edition, Hanser Verlag, Kunststoff 1996 , Examples are thermoplastic polyurethane elastomers (TPE-U or TPU), styrene-oligoblock copolymers (TPE-S) such as SBS (styrene-butadiene-styrene-oxy block copolymer) and SEES (styrene-ethylene-butylene-styrene block copolymer obtainable by hydrogenating SBS). , thermoplastic polyolefin elastomers (TPE-O), thermoplastic polyester elastomers (TPE-E), thermoplastic polyamide elastomers (TPE-A) and thermoplastic vulcanizates (TPE-V).
  • TPE-U or TPU thermoplastic polyurethane
  • polyacrylates examples include poly (meth) acrylates, which are preferably present as homopolymers or as block polymers. Such polymers are sold, for example, by Evonik under the trade name Degalan.
  • the additives be selected from the group consisting of the products of the copolymerization of PE or PP with maleic acid (anhydride) or acrylic acid.
  • the polymers employed as additives have a molecular weight of at most 200,000, preferably at most 170,000, more preferably at most 150,000 and even more preferably at most 130,000.
  • the compounds employed as additives have a molecular weight of at most 110,000, preferably at most 90,000, more preferably at most 70,000 and even more preferably at most 50,000.
  • carboxylic acids in particular embodiments also include, in particular, dicarboxylic acids, tricarboxylic acids and tetracarboxylic acids.
  • dicarboxylic acids are succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
  • the aforementioned carboxylic acid derivatives are especially aligned with carboxylic esters.
  • Examples of the aforementioned fatty acids are capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, nonadecanoic acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, undecylenic acid, palmitoleic acid, elaidic acid, vaccenic acid, icosenoic acid, cetoleic acid, erucic acid, nervonic acid, sorbic acid , Linoleic acid, linolenic acid, elaeostearic acid, arachidonic acid, timnodonic acid, clupanodonic acid, docosahexaenoic acid, stearic acid and oleic acid.
  • the additives include no stearic acid and oleic acid and preferably no saturated and unsaturated C 18 carboxylic acids, more preferably no saturated and unsaturated C 14 to C 18 carboxylic acids, even more preferably no saturated and unsaturated C 12 to C 18 carboxylic acids and most preferably no saturated and unsaturated C10 to C20 carboxylic acids.
  • C followed by a number in the context of the present invention refers to the carbon atoms contained in a molecule or molecular component, the number representing the number of carbon atoms.
  • substituted in the context of the present invention describes that at least one hydrogen atom of the group in question by a halogen, hydroxy, cyano, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C1-C5 alkanoyl , C3-C8 cycloalkyl, heterocyclic, aryl, heteroaryl, C1-C7 alkylcarbonyl, C1-C7 alkoxy, C2-C7 alkenyloxy, C2-C7 alkynyloxy, aryloxy, acyl, C1-C7 acryloxy, C1- C7 methacryloxy, C1-C7 epoxy, C1-C7 vinyl, C1-C5 alkoxycarbonyl, aroyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminarbonyloxy, C1-C7 alkylaminocarbonyloxy, C
  • cycloalkyl group and “heterocycloalkyl group” within the meaning of the present invention include saturated, partially saturated and unsaturated Systems other than aromatic systems referred to as “aryl groups” or “heteroaryl groups”.
  • alkyl in the context of the present invention is, unless stated otherwise, preferably straight or branched C1 to C27, more preferably straight or branched C1 to C25 and even more preferably straight or branched C1 to C20 carbon chains.
  • alkenyl and alkynyl in the context of the present invention are, unless stated otherwise, preferably straight or branched C2 to C27, more preferably straight or branched C2 to C25 and even more preferably straight or branched C2 to C20 carbon chains.
  • aryl in the context of the present invention stands for aromatic carbon rings, preferably for aromatic carbon rings having at most 7 carbon atoms, more preferably for the phenyl ring, wherein the abovementioned aromatic carbon rings may be part of a fused ring system.
  • aryl groups are phenyl, hydroxyphenyl, biphenyl and naphthyl.
  • heteroaryl in the context of the present invention stands for aromatic rings in which formally a carbon atom of an analogous aryl ring has been replaced by a heteroatom, preferably against an atom selected from the group consisting of O, S and N.
  • silanes are characterized by a structure of the formula (II): R p SiX (4-p) (II), wherein p is 0, 1, 2 or 3, X may be the same or different and is hydrogen, hydroxy, halogen or NR ' 2 , R' may be the same or different and is hydrogen, a substituted or unsubstituted C1-C9 alkyl group or a is substituted or unsubstituted aryl group and R may be the same or different and is selected from the group consisting of C 1 -C 30 alkyl groups, C 2 -C 30 alkenyl groups, C 2 -C 30 alkynyl groups, C 5 -C 30 Aryl groups, C6-C30 arylalkyl groups, C4-C30 heteroaryl groups, C5-C30 heteroarylalkyl groups, C3-C30 cycloalkyl groups, C4-C30 cycloalkylalkyl groups, C2-C30 hetero
  • the additive may, for example, be bound chemically or physically to the surface of the particles of the powdered coating material. In this case, it is not necessary for a complete surface coverage of the particles to take place, although this is preferred in certain embodiments of the present invention.
  • the additives are bonded as lightly as possible to the surface of the particles of the powdery coating material.
  • the additives used according to the invention do not bear a functional group.
  • the term "functional group" in the sense of the present invention denotes molecular groups in molecules that significantly influence the material properties and the reaction behavior of the molecules. Examples of such functional groups are: carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, silane groups, carbonyl groups, hydroxyl groups, amine groups, hydrazine groups, halogen groups and nitro groups.
  • the additives can not be easily removed from the surface due to friction, for example.
  • the additives used according to the invention carry at least one functional group, preferably at least two functional groups, more preferably at least three functional groups.
  • the inventors have surprisingly found that when using the powdery coating materials coated with an additive according to the invention, it is also possible to use coating materials with an unexpectedly high melting point. Without intending to be construed as limiting the invention, it is the view of the inventors that the more uniform delivery of the particles, with a reduced tendency to agglomerate, allows the particles to impinge on the substrate surface sporadically and completely absorb the kinetic energy present to deform the particle can be used. In the case of an uneven, ie localized, application of agglomerates, a part of the kinetic energy is apparently consumed by the breaking up of the agglomerate and later impacting particles are cushioned by coating material already present at this point but not yet solidified. Further, if the powdery coating material is previously passed through a flame, the thermal energy is likely to be better transmitted to the particles with evenly charged particles without agglomerates.
  • powdered coating materials coated with at least one additive according to the invention can also be used to produce homogeneous layers if the melting point of the coating material measured in [K] is up to 50%, preferably up to 60%, more preferably up to 65% and still more preferably up to 70% of the temperature measured in [K] of the medium used in the coating process, for example the gas flow, the combustion flame and / or the plasma flame, directed to the substrate.
  • At least one additive coated powdered coating materials are also used for the preparation of homogeneous layers, when measured in [K] melting point of the coating material up to 75%, preferably up to 80%, more preferably up to 85% and even more preferably up to 90% of in [K] measured temperature of the medium used in the coating process directed to the substrate, for example, the gas stream, the combustion flame and / or the plasma flame is.
  • the abovementioned percentages refer to the ratio of the melting temperature of the coating material to the temperature of the gas stream in cold gas spraying, the combustion flame in flame spraying and high-speed flame spraying or the plasma flame in non-thermal or thermal plasma spraying in [K].
  • the term "homogeneous layer” in the sense of the present invention describes that the relevant coating is less than 10%, preferably less than 5%, more preferably less than 3%, even more preferably less than 1% and most preferably less than 0, Have 1% cavities. In particular, it is preferred that no cavities are to be recognized.
  • the aforementioned term "cavity" in the sense of the present invention describes the proportion of the gaps enclosed in the coating on the two-dimensional surface of a transverse section of the coated substrate, based on the coating contained in the two-dimensional surface. A determination of this proportion is carried out by means of SEM at 30 randomly selected points of the coating produced according to the invention, wherein, for example, a length of 100 ⁇ m of the substrate coating is considered.
  • the use of the coating material and the additive not only provides improved conveyability of powdered coating materials, but also not yet conveyable powdered coating materials can be conveyed in a simple manner and used for the production of high-quality coatings.
  • the determination of the size distribution of the particles is preferably carried out by means of laser granulometry.
  • the particles can be measured in the form of a powder.
  • the scattering of the irradiated laser light is detected in different spatial directions and evaluated according to the Fraunhofer diffraction theory.
  • the particles are treated mathematically as spheres.
  • the determined diameters always relate to the equivalent spherical diameter determined over all spatial directions, irrespective of the actual shape of the particles.
  • It determines the size distribution which is calculated in the form of a volume average, based on the equivalent spherical diameter.
  • This volume-averaged size distribution can be represented as a cumulative frequency distribution.
  • the cumulative frequency distribution is simplified by various characteristic values, for example the D 10 , D 50 or D 90 value.
  • the measurements can be carried out, for example, using the particle size analyzer HELOS from Sympatec GmbH, Clausthal-Zellerfeld, Germany.
  • the dispersion of a dry powder can take place here with a dispersion unit of the Rodos T4.1 type at a primary pressure of, for example, 4 bar.
  • size distribution curve of the particles can be measured, for example, with a device from the company Quantachrome (device: Cilas 1064) according to the manufacturer's instructions.
  • 1.5 g of the powdered coating material are suspended in about 100 ml of isopropanol, treated for 300 seconds in an ultrasonic bath (apparatus: Sonorex IK 52, Fa.
  • the powdery coating material has a particle size distribution with a D 50 value of at most 53 ⁇ m, preferably at most 51 ⁇ m, more preferably at most 50 ⁇ m and even more preferably at most 49 ⁇ m.
  • the powdery coating material has a particle size distribution with a D 50 value of at most 48 ⁇ m, preferably at most 47 ⁇ m, more preferably at most 46 ⁇ m and even more preferably at most 45 ⁇ m.
  • D 50 in the sense of the present invention denotes the particle size at which 50% of the aforementioned volume-average particle size distribution determined by means of laser granulometry is below the stated value.
  • the measurements can be carried out, for example, according to the abovementioned measuring method using a particle size analyzer HELOS from Sympatec GmbH, Clausthal-Zellerfeld, Germany.
  • the powdered coating material has a particle size distribution with a D 50 value of at least 1.5 ⁇ m, preferably at least 2 ⁇ m, more preferably at least 4 ⁇ m and even more preferably at least 6 ⁇ m.
  • the powdery coating material has a particle size distribution with a D 50 value of at least 7 ⁇ m, preferably at least 9 ⁇ m, more preferably at least 11 ⁇ m and even more preferably at least 13 ⁇ m.
  • the powder has a particle size distribution with a D 50 value in the range from 1.5 to 53 ⁇ m, preferably in the range of 2 to 51 ⁇ m, more preferably in the range of 4 to 50 ⁇ m, and even more preferably in the range of 6 to 49 ⁇ m.
  • the powder has a particle size distribution with a D 50 value in the range of 7 to 48 ⁇ m, preferably in the range of 9 to 47 ⁇ m, more preferably in the range of 11 to 46 ⁇ m and even more preferably in the range of 13 to 45 microns.
  • the powder has a particle size distribution with a D 50 value in the range of 1.5 to 45 .mu.m, preferably in the range of 2 to 43 .mu.m, more preferably in the range of 2.5 to 41 .mu.m and even more preferably in the range of 3 to 40 microns.
  • the powder has a particle size distribution with a D 50 value in the range of 3.5 to 38 ⁇ m, preferably in the range of 4 to 36 ⁇ m, more preferably in the range of 4.5 to 34 and more preferably in the range of 5 to 32 microns.
  • the powder has a particle size distribution with a D 50 value in the range of 9 to 53 microns, preferably in the range of 12 to 51 microns, more preferably in the range of 15 to 50 microns, even more preferably in the range of 17 to 49 microns.
  • the powder has a particle size distribution with a D 50 value in the range of 19 to 48 ⁇ m, preferably in the range of 21 to 47 ⁇ m, more preferably in the range of 23 to 46 ⁇ m and even more preferably in the range of 25 to 45 microns.
  • the powdery coating material has a particle size distribution with a D 90 value of at most 103 ⁇ m, preferably at most 99 ⁇ m, more preferably at most 95 ⁇ m, even more preferably at most 91 ⁇ m, and most preferably at most 87 ⁇ m.
  • the powdery coating material has a D 90 value of at most 83 ⁇ m, preferably at most 79 ⁇ m, more preferably at most 75 ⁇ m, and still more preferably at most 71 ⁇ m.
  • D 90 in the sense of the present invention denotes the particle size at which 90% of the aforementioned volume-average particle size distribution determined by means of laser granulometry is below the stated value.
  • the measurements can be carried out, for example, according to the abovementioned measuring method using a particle size analyzer HELOS from Sympatec GmbH, Clausthal-Zellerfeld, Germany.
  • the powdery coating material has a particle size distribution with a D 90 value of at least 9 ⁇ m, preferably at least 11 ⁇ m, more preferably at least 13 ⁇ m and even more preferably at least 15 ⁇ m.
  • the powdered coating material has a particle size distribution having a D 90 value of at least 17 ⁇ m, preferably at least 19 ⁇ m, more preferably at least 21 ⁇ m and even more preferably at least 22 ⁇ m.
  • the powdery coating materials have a particle size distribution with a D 90 value in the range of 42 to 103 ⁇ m, preferably in the range of 45 to 99 ⁇ m, more preferably in the range of 48 to 95 ⁇ m and even more preferably in the range of 50 to 91 microns.
  • the powdered coating material have a D 90 value in the range of 52 to 87 microns, preferably in the range of 54 to 81 microns, more preferably in the range of 56 to 75 microns, and even more preferably in Range of 57 to 71 microns has.
  • the powdery coating material has a particle size distribution with a D 10 value of at most 5 ⁇ m, preferably at most 4 ⁇ m, more preferably at most 3 ⁇ m and even more preferably at most 2.5 ⁇ m.
  • the powdery coating material has a grain size distribution having a D 10 value of at most 2.2 ⁇ m, preferably at most 2 ⁇ m, more preferably at most 1.8 ⁇ m, and still more preferably at most 1.7 ⁇ m having.
  • D 10 in the sense of the present invention denotes the particle size at which 10% of the aforementioned volume-average particle size distribution determined by means of laser granulometry is below the stated value.
  • the measurements can be carried out, for example, according to the abovementioned measuring method using a particle size analyzer HELOS from Sympatec GmbH, Clausthal-Zellerfeld, Germany.
  • the additive-containing powdery coating materials with a high fines content still strongly to the formation of fine dusts, whereby the handling of corresponding powder clearly is difficult.
  • the additive-containing, powdery coating material has a particle size distribution with a D 10 value of at least 0.2 ⁇ m, preferably at least 0.4 ⁇ m, more preferably at least 0.5 ⁇ m and even more preferably at least 0, 6 microns have.
  • the additive-containing, powdery coating material has a particle size distribution with a D 10 value of at least 0.7 ⁇ m, preferably 0.8 ⁇ m, more preferably 0.9 ⁇ m and even more preferably at least 1, 0 microns.
  • the additive-coated, powdery coating material is characterized in that it has a particle size distribution with a D 10 value from a range of 0.2 to 5 microns, preferably from a range of 0.4 to 4 microns, more preferably from a Range of 0.5 to 3 microns, and more preferably from a range of 0.6 to 2.5 microns.
  • the additive-coated, powdery coating material has a particle size distribution with a D 10 value from a range from 0.7 to 2.2 ⁇ m, preferably from a range from 0.8 to 2.1 ⁇ m more preferably from a range of 0.9 to 2.0 microns and even more preferably from a range of 1.0 to 1.9 microns
  • the powdered coating material has a particle size distribution with a D 10 value of 3.7 to 26 ⁇ m, a D 50 value of 6 to 49 ⁇ m and a D 90 value of 12 to 86 ⁇ m having.
  • the powdery coating material has a particle size distribution with a D 10 value of 5.8 to 26 ⁇ m, a D 50 value of 11 to 46 ⁇ m and a D 90 value of 16 to 83 microns having.
  • the powdery coating material has a particle size distribution with a D 10 value of 9 to 19 ⁇ m, a D 50 value of 16 to 35 ⁇ m and a D 90 value of 23 to 72 ⁇ m having.
  • the powdery coating material has a particle size distribution with a D 10 value of 0.8 to 28 ⁇ m, a D 50 value of 1.5 to 45 ⁇ m and a D 90 value of 2, 5 to 81 microns.
  • the powdery coating material has a particle size distribution with a D 10 value of 2.2 to 22 ⁇ m, a D 50 value of 4 to 36 ⁇ m and a D 90 value of 4 to 62 has ⁇ m.
  • the powdery coating material has a particle size distribution with a D 10 value of 2.8 to 17 ⁇ m, a D 50 value of 6 to 28 ⁇ m and a D 90 value of 9 to 49 microns has.
  • the powdered coating material has a particle size distribution with a D 10 value of 4.8 to 29 microns, a D 50 value 9-53 microns and a D 90 value of 13 to 97 microns having.
  • the powdery coating material has a particle size distribution with a D 10 value of 12 to 26 ⁇ m, a D 50 value of 23 to 46 ⁇ m and a D 90 value of 35 to 87 ⁇ m , In certain of the aforementioned embodiments, it is even more preferable that the powdery coating material has a particle size distribution with a D 10 value of 15 to 24 ⁇ m, a D 50 value of 28 to 44 ⁇ m and a D 90 value of 41 to 78 ⁇ m having.
  • the conveyability of the additive-containing, powdery coating material is dependent on the width of the particle size distribution.
  • the span of the powdery coating material is therefore at most 2.9, preferably at most 2.6, more preferably at most 2.4, and even more preferably at most 2.1.
  • the span of the powdery coating material is at most 1.9, preferably at most 1.8, more preferably at most 1.7, and even more preferably at most 1.6.
  • the span value of the powdery coating material is therefore 0.4, preferably at least 0.5, more preferably at least 0.6 and even more preferably at least 0.7.
  • the span value of the powdered coating material is at least 0.8, preferably at least 0.9, more preferably at least 1.0 and even more preferably at least 1.1.
  • the powdered coating material may have a span value in the range of 0.4 to 2.9, preferably in the range of 0.5 to 2.6, more preferably in the range of 0.6 to 2, 4 and more preferably in the range of 0.7 to 2.1.
  • the powdery coating material has a span value in the range of 0.8 to 1.9, preferably in the range of 0.9 to 1.8, more preferably in the range of 1.0 to 1.7 and more preferably in the range of 1.1 to 1.6.
  • the powdery coating material has a particle size distribution with a span in the range from 0.4 to 2.9 and a D 50 value in the range from 1.5 to 53 ⁇ m, preferably in the range from 2 to 51 ⁇ m, more preferably in the range from 4 to 50 ⁇ m, more preferably in the range of 6 to 49 ⁇ m, and most preferably in the range of 7 to 48 ⁇ m.
  • the powdery coating material has a particle size distribution with a span in the range of 0.5 to 2.6 and a D 50 value in the range of 1.5 to 53 microns, preferably in the range of 2 to 51 microns, more preferably in the range of 4 to 50 ⁇ m, more preferably in the range of 6 to 49 ⁇ m, and most preferably in the range of 7 to 48 ⁇ m.
  • the powdery coating material has a particle size distribution with a span in the range of 0.6 to 2.4 and a D 50 value in the range of 1.5 to 53 .mu.m, preferably in the range of 2 to 51 .mu.m, more preferably in the range of 4 to 50 ⁇ m, more preferably in the range of 6 to 49 ⁇ m, and most preferably in the range of 7 to 48 ⁇ m.
  • the powdery coating material has a particle size distribution with a span in the range of 0.7 to 2.1 and a D 50 value in the range of 1.5 to 53 ⁇ m, preferably in the range of 2 to 51 ⁇ m, more preferably in the range of 4 to 50 ⁇ m, more preferably in the range of 6 to 49 ⁇ m, and most preferably in the range of 7 to 48 ⁇ m.
  • the density of the powdery coating material can have an influence on the promotion of such powders in the form of an aerosol. Without intending to be construed as limiting the invention, it is the view of the inventors that the differences in inertia of equally sized particles of different density will result in a different behavior of the aerosol streams of powdered coating materials having identical grain size distribution. Therefore, it may be difficult to transfer production processes that have been optimized for a specific D 50 to different density powdered coating materials. In certain embodiments, it is therefore preferable that the upper limit of the span value is corrected depending on the density of the powdery coating material used.
  • spa n OK spa n O ⁇ ⁇ Alu ⁇ X 1 3
  • Span OK is the corrected upper span value
  • Span O is the upper span value
  • ⁇ Alu is the density of aluminum (2.7 g / cm 3 )
  • ⁇ X is the density of the powdered coating material used.
  • Coating processes which can be used according to the invention are known to the person skilled in the art under the name of cold gas spraying, thermal plasma spraying, non-thermal plasma spraying, flame spraying and high-speed flame spraying.
  • the cold gas spraying is characterized in that the powder to be applied is not melted in the gas jet, but that the particles are greatly accelerated and form a coating on the surface of the substrate due to their kinetic energy.
  • gases known to those skilled in the art can be used as the carrier gas, such as nitrogen, helium, argon, air, krypton, neon, xenon, carbon dioxide, oxygen or mixtures thereof. In certain variants, it is particularly preferred that are used as gas, air, helium or mixtures thereof.
  • a controlled expansion of the aforementioned gases in a corresponding nozzle gas velocities of up to 3000 m / s can be achieved.
  • the particles can be accelerated up to 2000 m / s.
  • a powder is converted into the liquid or plastic state by means of a flame and then applied as a coating to a substrate.
  • a flame e.g. a mixture of oxygen and a combustible gas such as acetylene or hydrogen burned.
  • part of the oxygen is used to convey the powdery coating material into the combustion flame.
  • the particles reach in conventional variants of this process speeds between 24 to 31 m / s.
  • high-speed flame spraying converts a powder into a liquid or plastic state by means of a flame.
  • the particles are accelerated significantly faster compared to the aforementioned method.
  • a velocity of the gas stream of 1220 to 1525 m / s is called with a velocity of the particles of about 550 to 795 m / s.
  • gas velocities of over 2000 m / s are achieved.
  • the speed of the flame is between 1000 and 2500 m / s.
  • the flame temperature is between 2200 ° C and 3000 ° C.
  • the temperature of the flame is thus comparable to the temperature during flame spraying. This is achieved by combustion of the gases under a pressure of about 515 to 621 kPa followed by the expansion of the combustion gases in a nozzle.
  • coatings produced thereby have a higher density compared to, for example, coatings obtained by the flame spraying process.
  • the detonation / explosive flame spraying can be regarded as a subspecies of the high-velocity flame spraying.
  • the powdery coating material is greatly accelerated by repeated detonations of a gas mixture such as acetylene / oxygen, for example, particle velocities of about 730 m / s are achieved.
  • the detonation frequency of the method is in this case for example between approximately 4 to 10 Hz. In variants such as the so-called high-frequency gas detonation spraying, however, detonation frequencies of approximately 100 Hz are also selected.
  • the resulting layers should usually have a particularly high hardness, strength, density and good bonding to the substrate surface.
  • a disadvantage of the aforementioned method the increased security costs, and, for example, the large noise pollution due to the high gas velocities.
  • thermal plasma spraying for example, a primary gas such as argon is passed through a DC arc furnace at a rate of 40 l / min and a secondary gas such as hydrogen at a rate of 2.5 l / min, thereby generating a thermal plasma.
  • the feed of, for example, 40 g / min of the powdery coating material is then carried out with the aid of a carrier gas stream which is passed into the plasma flame at a rate of 4 l / min.
  • the delivery rate of the powdered coating material is between 5 g / min and 60 g / min, more preferably between 10 g / min and 40 g / min.
  • argon, helium or mixtures thereof as ionizable gas.
  • the total gas flow is also preferably 30 to 150 SLPM (standard liters per minute) for certain variants.
  • the electrical power used for the ionization of the gas flow without the heat energy dissipated as a result of cooling can be selected, for example, between 5 and 100 kW, preferably between 40 and 80 kW. In this case, plasma temperatures between 4000 K and a few 10000 K can be achieved.
  • a non-thermal plasma is used to activate the powdery coating material.
  • the plasma used in this case is generated for example with a barrier discharge or corona discharge with a frequency of 50 Hz to 1 MHz. In certain variants of non-thermal plasma spraying, it is preferred to operate at a frequency of 10 kHz to 100 kHz.
  • the temperature of the plasma is preferably less than 3000 K, preferably less than 2500 K and more preferably less than 2000 K. This minimizes the technical complexity and keeps the energy input in the applied coating material as low as possible, which in turn allows a gentle coating of the substrate , The magnitude of the temperature of the plasma flame is thus preferably comparable to that in flame spraying or high-speed flame spraying.
  • Targeted choice of parameters also allows the generation of nonthermal plasmas with a core temperature below 1173 K or even below 773 K in the core region.
  • the measurement of the temperature in the core region takes place here, for example, with a thermocouple type NiCr / Ni and a tip diameter of 3 mm in 10 mm distance from the nozzle exit in the core of the exiting plasma jet at ambient pressure.
  • Such non-thermal plasmas are particularly suitable for coatings of very temperature-sensitive substrates.
  • the outlet opening of the plasma flame to make such that the web widths of the coatings produced are between 0.2 mm and 10 mm.
  • This allows a very accurate, flexible, energy-efficient coating with the best possible utilization of the coating material used.
  • a distance of the spray lance to the substrate for example, a distance of 1 mm is selected. This allows for the greatest possible flexibility of the coatings while ensuring high-quality coatings.
  • the distance between the spray lance and the substrate is between 1 mm and 35 mm.
  • ionizable gas various gases known to those skilled in the art and mixtures thereof can be used in the non-thermal plasma process. Examples of these are helium, argon, xenon, nitrogen, oxygen, hydrogen or air, preferably argon or air. A particularly preferred ionizable gas is air.
  • the speed of the plasma flow is below 200 m / s.
  • a flow rate for example, a value between 0.01 m / s and 100 m / s, preferably between 0.2 m / s and 10 m / s are selected.
  • the volume flow of the carrier gas is between 10 and 25 l / min, more preferably between 15 and 19 l / min.
  • the particles of the powdery coating material are preferably metallic particles or metal-containing particles.
  • the metal content of the metallic Particles or metal-containing particles at least 95 wt .-%, preferably at least 99 wt .-%, even more preferably at least 99.9 wt .-% is.
  • the metal or metals are selected from the group consisting of silver, gold, platinum, palladium, vanadium, chromium, manganese, cobalt, germanium, antimony, aluminum, zinc, tin, iron, copper, nickel, titanium, silicon , Alloys and mixtures thereof.
  • the metal or metals be selected from the group consisting of silver, gold, aluminum, zinc, tin, iron, copper, nickel, titanium, silicon, alloys, and mixtures thereof, preferably from the group consisting of silver, gold, aluminum, zinc, tin, iron, nickel, titanium, silicon, alloys and mixtures thereof.
  • the metal or the metals of the particles of the powdery coating material is selected from the group consisting of silver, aluminum, zinc, tin, copper, alloys and mixtures thereof.
  • Particularly suitable particles in specific embodiments have been found to be metallic particles or metal-containing particles in which the metal or metals are selected from the group consisting of silver, aluminum and tin.
  • the powdery coating material consists of inorganic particles, which are preferably selected from the group consisting of carbonates, oxides, hydroxides, carbides, halides, nitrides and mixtures thereof. Particularly suitable are mineral and / or metal oxide particles.
  • the inorganic particles are alternatively or additionally selected from the group consisting of carbon particles or graphite particles.
  • Another possibility is the use of mixtures of the metallic particles and the aforementioned inorganic particles, such as mineral and / or metal oxide particles, and / or the particles selected from the group consisting of carbonates, oxides, hydroxides, carbides, halides, nitrides and mixtures thereof.
  • the powdery coating material may include or consist of glass particles. In certain embodiments, it is particularly preferred that the powdered coating material comprises or consists of coated glass particles.
  • the powdered coating material comprises or consists of organic and / or inorganic salts.
  • the powdery coating material comprises or consists of plastic particles.
  • the abovementioned plastic particles are formed from, for example, pure or mixed homo-, co-, block- or prepolymers or mixtures thereof.
  • the plastic particles may be pure crystals or be mixed crystals or have amorphous phases.
  • the plastic particles can be obtained, for example, by mechanical comminution of plastics.
  • the powdery coating material comprises or consists of mixtures of particles of different materials.
  • the powdery coating material consists in particular of at least two, preferably three, different particles of different materials.
  • the particles can be produced by different methods.
  • the metal particles can be obtained by atomization or atomization of molten metal.
  • Glass particles can be produced by mechanical comminution of glass or else from the melt. In the latter case, the molten glass can also be atomized or atomized. Alternatively, molten glass can also be cut on rotating elements, such as a drum.
  • Mineral particles, metal oxide particles and inorganic particles selected from the group consisting of oxides, hydroxides, carbonates, carbides, nitrides, halides and mixtures thereof can be obtained by comminuting the naturally occurring minerals, rocks, etc. and subsequently size-classified.
  • Size classification can be carried out, for example, by means of cyclones, air separators, screening, etc.
  • the particles of powdered coating material have been coated before being coated with the additive.
  • the aforesaid coating may comprise or be made of a metal.
  • a coating of a particle may be closed or particulate, with closed structure coatings being preferred.
  • the layer thickness of such a metallic coating is preferably less than 1 ⁇ m, more preferably less than 0.8 ⁇ m and even more preferably less than 0.5 ⁇ m.
  • such coatings have a thickness of at least 0.05 ⁇ m, more preferably at least 0.1 ⁇ m.
  • particularly preferred metals for use in any of the foregoing coatings are selected from the group consisting of copper, titanium, gold, silver, tin, zinc, iron, silicon, nickel, and aluminum, preferably selected from the group of gold, silver, tin and zinc, more preferably from the group consisting of silver, tin and zinc.
  • the term main constituent in the sense of the abovementioned coating denotes that the metal in question or a mixture of the abovementioned metals represents at least 90% by weight, preferably 95% by weight, more preferably 99% by weight, of the metal content of the coating. It must be understood that in the case of a partial oxidation of the oxygen content of the corresponding oxide layer is not included.
  • the production of such metallic coatings can be carried out, for example, by means of gas-phase synthesis or wet-chemical processes.
  • the particles of the powdery coating material according to the invention are additionally or alternatively coated with a metal oxide layer.
  • this metal oxide layer consists essentially of silicon oxide, aluminum oxide, boron oxide, zirconium oxide, cerium oxide, iron oxide, titanium oxide, chromium oxide, tin oxide, molybdenum oxide, their hydrated oxides, their hydroxides and mixtures thereof.
  • the metal oxide layer consists essentially of silicon oxide.
  • the aforementioned term "consists essentially of" in the sense of the present invention means that at least 90%, preferably at least 95%, more preferably at least 98%, even more preferably at least 99% and most preferably at least 99.9% of the metal oxide layer the aforementioned metal oxides, in each case based on the number of particles of the metal oxide layer, wherein optionally contained water is not included.
  • the determination of the composition of the metal oxide layer can be carried out by methods known to the person skilled in the art, for example sputtering in combination with XPS or TOF-SIMS.
  • the metal oxide layer is not an oxidation product of a metal core located thereunder.
  • the application of such a metal oxide layer can be carried out, for example, by the sol-gel method.
  • the substrate is selected from the group consisting of plastic substrates, inorganic substrates, cellulosic substrates, and mixtures thereof.
  • the plastic substrates may be, for example, plastic films or molded plastic.
  • the shaped bodies can have geometrically simple or complex shapes.
  • the plastic molding may be, for example, a component of the automotive industry or the construction industry.
  • the cellulose-containing substrates may be cardboard, paper, wood, wood-containing substrates, etc.
  • the inorganic substrates may be, for example, metallic substrates, such as metal sheets or metallic moldings or ceramic or mineral substrates or moldings.
  • the inorganic substrates may also be solar cells or silicon wafers onto which, for example, electrically conductive coatings or contacts are applied.
  • Substrates made of glass can also be used as inorganic substrates.
  • the glass, in particular glass panes can be provided using the method according to the invention, for example with electrochromic coatings.
  • coated by the process according to the invention substrates are suitable for very different applications.
  • the coatings have optical and / or electromagnetic effects.
  • the coatings can cause reflections or absorptions.
  • the coatings may be electrically conductive, semi-conductive or non-conductive.
  • Electrically conductive layers can be applied to components, for example in the form of printed conductors. This can be used, for example, to enable the power supply in the context of the electrical system in a motor vehicle component. Furthermore, however, such a track may also be shaped, for example, as an antenna, as a shield, as an electrical contact, etc. This is for example particularly advantageous for RFID applications (radio frequency identification). Furthermore, coatings according to the invention can be used, for example, for heating purposes or for specific heating of special components or special parts of larger components.
  • the coatings produced serve as slip layers, diffusion barriers for gases and liquids, wear and / or corrosion protection layers. Furthermore, the coatings produced can influence the surface tension of liquids or have adhesion-promoting properties.
  • the coatings produced according to the invention can furthermore be used as sensor surfaces, for example as a human-machine interface (HMI: human-machine interface), for example in the form of a touch screen.
  • HMI human-machine interface
  • the coatings can be used to shield from electromagnetic interference (EMI) or to protect against electrostatic discharge (ESD).
  • EMI electromagnetic interference
  • ESD electrostatic discharge
  • the coatings can also be used to effect electromagnetic compatibility (EMC).
  • layers can be applied by the use of the particles according to the invention, which are applied, for example, to increase the stability of corresponding components after their repair.
  • An example is repairs in the aircraft sector, for example, a loss of material due to processing steps must be compensated or a coating is to be applied, for example, for stabilization. This proves difficult for aluminum components, for example, and usually requires finishing operations such as sintering.
  • firmly adhering coatings can be applied under very gentle conditions, even without post-processing steps such as sintering being necessary.
  • the coatings serve as electrical contacts and permit electrical connection between different materials.
  • Figures 1 and 2 show a wafer coated with solar contact paste, which was coated with a powdery coating material according to the invention using the non-thermal plasma spraying according to Example 14.
  • the size distribution of the particles of the powdered coating materials used was determined by means of a HELOS instrument (Sympatec, Germany). For the measurement, 3 g of the powdered coating material was placed in the meter and sonicated for 30 seconds prior to measurement. For dispersion, a Rodos T4.1 dispersion unit was used, the primary pressure being 4 bar. The evaluation was carried out with the standard software of the device.
  • Example 1 powdery coating materials coated with acrylic polymer (poly (iso-butyl methacrylate))
  • Example 2 Ethyl cellulose coated, powdery coating materials
  • the application of the additive was carried out analogously to Example 1.
  • the additive used was 1 g of ethylcellulose (Ethocel Standard 10, Dow Wolff Cellulosics).
  • Example 3 powdery coating materials coated with acrylic polymer (methyl methacrylate)
  • the application of the additive was carried out analogously to Example 1.
  • the additive used was 2 g of an acrylic polymer based on methyl methacrylate and n-butyl methacrylate (Degalan LP AL 23, FA Evonik).
  • Example 4 powdery coating materials coated with 1,10-decanedicarboxylic acid
  • the application of the coating aid was carried out analogously to Example 4.
  • As a coating aid 3 g of monoethyl fumarate was used.
  • Example 6 powdery coating materials coated with adipic acid monoethyl ester
  • the application of the coating aid was carried out analogously to Example 4.
  • coating assistant 3 g of adipic acid monoethyl ester were used.
  • Example 7 powdery coating materials coated with methyltriglycol
  • the application of the coating aid was carried out analogously to Example 4.
  • coating assistant 3 g of methyltriglycol were used.
  • Example 8 powdered coating materials coated with adipic acid monoethyl ester
  • the application of the coating aid was carried out analogously to Example 4. Here, however, copper particles were used with a D 50 of 34 microns.
  • As coating assistant 3 g of adipic acid monoethyl ester were used.
  • Example 9 powdery coating materials coated with methyltriglycol
  • the application of the coating aid was carried out analogously to Example 4. Here, however, a copper particle was used with a D 50 of 34 microns.
  • As coating assistant 3 g of methyltriglycol were used.
  • Example 10 Ethocel coated, powdery coating materials
  • the application of the coating aid was carried out analogously to Example 4. In this case, a copper particle with a D 50 value of 34 microns was used.
  • coating assistant 3 g of ethylcellulose (Ethocel Standard 10, Dow Wolff Cellulosics) were used.
  • Example 11 Monoethyl fumarate-coated, powdery coating materials
  • the application of the coating aid was carried out analogously to Example 4. In this case, a copper particle with a D 50 value of 34 microns was used.
  • coating assistant 3 g of DEGALAN PM 381 (copolymer of methyl methacrylate and isobutyl methacrylate, Evonik) were used.
  • Example 12 powdery coating materials coated with Aerosil 200
  • the application of the additive was carried out analogously to Example 4.
  • 100 g of spherical tin particles were used with a D 50 of 28 microns.
  • 3 g of Aerosil 200 (fumed silica, Evonik) were used as the additive.
  • Example 14 Non-thermal plasma spraying of tin particles
  • the application of the powdery coating material was carried out by means of a Plasmatron plant from Inocon, Attnang-Puchheim, Austria. Nitrogen was used as the ionizable gas. Standard process parameters were used. The substrate used was wafers coated with a solar contact paste. As powdery coating materials were used with additive-coated tin particles according to Example 12 and analogous tin particles without additive.
  • Example 15 Flame Spraying of Powder Coating Materials According to Examples 4 to 11
  • coated sheets according to the invention were much more homogeneous in terms of their appearance and feel. SEM images of the surfaces show the formation of larger uniform areas of the coating, while the surface of the comparative examples are characterized by a large number of separated particles. Furthermore, the cross-section shows that cavities contained in the coating of the sheet according to the invention are significantly smaller.

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EP12741313.6A 2011-07-25 2012-07-25 Verfahren zur substratbeschichtung und verwendung additivversehener, pulverförmiger beschichtungsmaterialien in derartigen verfahren Active EP2737100B1 (de)

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DE102011052119A DE102011052119A1 (de) 2011-07-25 2011-07-25 Verfahren zur Substratbeschichtung und Verwendung additivversehener, pulverförmiger Beschichtungsmaterialien in derartigen Verfahren
PCT/EP2012/064638 WO2013014213A2 (de) 2011-07-25 2012-07-25 Verfahren zur substratbeschichtung und verwendung additivversehener, pulverförmiger beschichtungsmaterialien in derartigen verfahren

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CN108950459A (zh) 2018-12-07
KR20140061422A (ko) 2014-05-21
WO2013014213A3 (de) 2013-06-13
WO2013014213A2 (de) 2013-01-31
CN103827344A (zh) 2014-05-28
JP2014527575A (ja) 2014-10-16
EP2737100A2 (de) 2014-06-04
US20140230692A1 (en) 2014-08-21

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