US20140230692A1 - Methods for Substrate Coating and Use of Additive-Containing Powdered Coating Materials in Such Methods - Google Patents

Methods for Substrate Coating and Use of Additive-Containing Powdered Coating Materials in Such Methods Download PDF

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Publication number
US20140230692A1
US20140230692A1 US14/234,851 US201214234851A US2014230692A1 US 20140230692 A1 US20140230692 A1 US 20140230692A1 US 201214234851 A US201214234851 A US 201214234851A US 2014230692 A1 US2014230692 A1 US 2014230692A1
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Prior art keywords
coating material
additive
particles
spraying
powdered coating
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US14/234,851
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English (en)
Inventor
Sebastian Hofener
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 DE102011052119A external-priority patent/DE102011052119A1/de
Priority claimed from DE102011052120A external-priority patent/DE102011052120A1/de
Application filed by Eckart GmbH filed Critical Eckart GmbH
Assigned to ECKART GMBH reassignment ECKART GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HOFENER, SEBASTIAN, GREB, MARCO, WOLFRUM, CHRISTIAN, RUPPRECHT, MARKUS, REIS, ANDREAS
Publication of US20140230692A1 publication Critical patent/US20140230692A1/en
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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
    • C23C4/065—
    • 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
    • C23C4/124—
    • C23C4/127—
    • 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 relates to the use of powdered coating materials for coating substrates. Furthermore, the present invention comprises methods for substrate coating using such powdered coating materials. Furthermore, the present invention comprises powdered coating materials which are suitable for the above-named uses and/or methods.
  • a large number of coating methods for different substrates are already known. For example, metals or precursors thereof are deposited on a substrate surface from the gas phase, see e.g. PVD or CVD methods. Furthermore, corresponding substances can be deposited for example from a solution by means of galvanic methods. In addition, it is possible to apply coatings for example in the form of varnishes to the surface.
  • all the methods have specific advantages and disadvantages. For example, in the case of deposition in the form of varnishes, large amounts of water and/or organic solvents are required, a drying time is needed, the coating material to be applied must be compatible with the base varnish, and a residue of the base varnish likewise remains on the substrate. For example, application by means of PVD methods requires large amounts of energy in order to bring non-volatile substances into the gas phase.
  • a large number of coating methods have been developed to provide the properties desired for the respective intended use.
  • Known methods use, for example, kinetic energy, thermal energy or mixtures thereof to produce the coatings, wherein the thermal energy can originate for example from a conventional combustion flame or a plasma flame.
  • the latter are further divided into thermal and non-thermal plasmas, by which is meant that a gas has been partially or completely separated into free charge carriers such as ions or electrons.
  • the coating is formed by applying a powder to a substrate surface, wherein the powder particles are greatly accelerated.
  • a heated process gas is accelerated to ultrasonic speed by expansion in a de Laval nozzle and then the powder is injected.
  • the particles form a dense layer when they strike the substrate surface.
  • WO 2010/003396 A1 discloses the use of cold gas spraying as a coating method for applying wear-protection coatings. Furthermore, disclosures of the cold gas spraying method are found for example in EP 1 363 811 A1, EP 0 911 425 B1 and U.S. Pat. No. 7,740,905 B2.
  • Flame spraying belongs to the group of thermal coating methods.
  • a powdered coating material is introduced into the flame of a fuel gas/oxygen mixture.
  • temperatures of up to approximately 3200° C. can be reached for example with oxyacetylene flames. Details of the method can be learned from publications such as e.g. EP 830 464 B1 and U.S. Pat. No. 5,207,382 A.
  • thermal plasma spraying a powdered coating material is injected into a thermal plasma.
  • temperatures of up to approx. 20,000 K are reached, whereby the injected powder is melted and deposited on a substrate as coating.
  • thermal plasma spraying and specific embodiments, as well as method parameters are known to a person skilled in the art.
  • reference is made to WO 2004/016821 which describes the use of thermal plasma spraying to apply an amorphous coating.
  • EP 0 344 781 for example discloses the use of flame spraying and thermal plasma spraying as coating methods using a tungsten carbide powder mixture.
  • Specific devices for use in plasma spraying methods are described multiple times in the literature, such as for example in EP 0 342 428 A2, U.S. Pat. No. 7,678,428 B2, U.S. Pat. No. 7,928,338 B2 and EP 1 287 898 A2.
  • a fuel is combusted under high pressure, wherein fuel gases, liquid fuels and mixtures thereof can all be used as fuel.
  • a powdered coating material is injected into the highly accelerated flame.
  • This method is known for being characterized by relatively dense spray coatings.
  • High-speed flame spraying is also well known to a person skilled in the art and has already been described in numerous publications.
  • EP 0 825 272 A2 discloses a substrate coating with a copper alloy using high-speed flame spraying.
  • WO 2010/037548 A1 and EP 0 492 384 A1 for example disclose the method of high-speed flame spraying and devices to be used therein.
  • Non-thermal plasma spraying is carried out largely analogously to thermal plasma spraying and flame spraying.
  • a powdered coating material is injected into a non-thermal plasma and deposited with it onto a substrate surface.
  • this method is characterized by a particularly low thermal load of the coated substrate.
  • EP 2 104 750 A2 describes the use of this method and a device for carrying it out.
  • DE 103 20 379 A1 describes the production of an electrically heatable element using this method.
  • a general problem of coating methods using a powdered coating material is the conveying of the powders.
  • a very uniform feeding in of the powdered coating material is necessary in particular to produce particularly thin layers for example.
  • various specially designed conveyor devices are additionally to be found as the subject of separate patent applications. Examples are found in WO 03/029762 A1 and WO 2011/032807 A1.
  • the object of the present invention is to make it possible to produce novel coatings or to improve the production of known coatings. Furthermore, an object of the present invention is to make it possible to produce particularly thin coatings of high quality. Furthermore, an object of the present invention is to solve existing problems with respect to the conveyability of the powdered coating material used in a coating method.
  • a further object of the present invention is to provide methods for substrate coating which are characterized by novel coatings or an improved quality of the coating.
  • a further object of the present invention is to provide a powdered coating material which is particularly suitable for one of the above-named uses in coating methods.
  • the present invention relates to the use of a particle-containing powdered coating material in a coating method, wherein the particles of the powdered coating material are at least partially provided with at least one additive and wherein the coating method is selected from the group consisting of cold gas spraying, flame spraying, high-speed flame spraying, thermal plasma spraying and non-thermal plasma spraying.
  • the weight proportion of the additive or additives is at most 32 wt.-%, relative to the total weight of the coating material and the additive.
  • the weight proportion of the additive or additives is between 0.02% and 32 wt.-%, in each case relative to the total weight of the coating material and the additive.
  • the carbon content of the additive-containing particles of the powdered coating material is from 0.01 wt.-% to 15 wt.-%, in each case relative to the total weight of the coating material and the additive.
  • the weight proportion of the additive or additives is at least 0.02 wt.-%, relative to the total weight of the coating material and the additive.
  • the compound used as additive has, or the compounds used as additive have, at least 6 carbon atoms.
  • the particles of the powdered coating material comprise 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 method is selected from the group consisting of flame spraying and non-thermal plasma spraying.
  • Non-thermal plasma spraying is particularly preferred.
  • the at least one additive comprises no stearic acid and/or oleic acid and preferably no saturated or unsaturated C18 carboxylic acids, more preferably no saturated or unsaturated C14 to C18 carboxylic acids, still more preferably no saturated or unsaturated C12 to C18 carboxylic acids and most preferably no saturated or unsaturated C10 to C20 carboxylic acids.
  • the additive is, or the additives are, selected from the group consisting of polymers, monomers, silanes, waxes, oxidized waxes, carboxylic acids, phosphonic acids, derivatives of the above-named and mixtures thereof.
  • the powdered coating material has a span value in the range of from 0.4 to 2.9, which is defined as follows:
  • the additive, or the additives can be removed from the coated particles using organic and/or aqueous solvent.
  • the powdered coating material has a particle-size distribution with a D 50 value in the range of from 1.5 to 53 ⁇ m.
  • the powdered coating material has a particle-size distribution with a D 90 value in the range of from 9 to 103 ⁇ m.
  • the powdered coating material has a particle-size distribution with a D 10 value in the range of from 0.2 to 5 ⁇ m.
  • the present invention relates to methods for coating a substrate selected from the group consisting of cold gas spraying, flame spraying, high-speed flame spraying, thermal plasma spraying and non-thermal plasma spraying, wherein a powdered coating material is used the particles of which are provided at least partially with at least one additive.
  • the method is is selected from the group consisting of flame spraying and non-thermal plasma spraying.
  • the method is preferably non-thermal plasma spraying in particular ones of the above-named embodiments.
  • the powdered coating material is conveyed as an aerosol.
  • the medium directed onto the substrate is air or has been produced from air.
  • the above-named air can be taken from the surrounding atmosphere.
  • the air is purified before it is used, wherein for example dust and/or water vapor is separated off.
  • the gaseous constituents of the air, other than nitrogen and oxygen are also largely separated off completely, wherein the total amount of the impurities is preferably ⁇ 0.01 vol.-%, further preferably ⁇ 0.001 vol.-%.
  • the term “powdered coating material” within the meaning of the present invention relates to a particle mixture which is applied to the substrate as coating.
  • the inventors are of the view that the effect of the applied additives is caused, among other things, by an effect as spacers between the individual particles, wherein an application to or a coverage of the surface beyond a particular extent is not associated with a markedly improved conveyability, but requires an increased use of the additive, or the additives, which therefore only gives rise to costs and thus is not economically worthwhile.
  • At most 90%, preferably at most 85%, more preferably at most 80%, still more preferably at most 75% and most preferably at most 70% of the surface of the particles is covered with the additive, or the additives.
  • a coverage of the surface of the particles provides a certain protective effect for example against oxidizing influences from the environment.
  • it is preferred that at least 20%, preferably at least 25%, more preferably at least 30% and still more preferably at least 35% of the surface of the particles is covered with the additive, or the additives.
  • At least 40%, preferably at least 50%, more preferably at least 55% and still more preferably at least 60% of the surface of the particles is covered with the additive, or the additives.
  • a determination of the surface coverage of the powdered coating materials according to the invention is carried out by means of SEM, wherein 30 randomly selected particles are examined.
  • the inventors have surprisingly found that the conveyability of a powdered coating material is significantly increased by at least partially covering the surface of the particles with at least one additive. This is of great importance in coating methods, in particular in 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 method and more uniform feeding in of the powdered coating material furthermore makes it possible to produce much more homogeneous coatings with few defects and a very high degree of cross-linking of the particles.
  • Such features are important in particular for the production of particularly thin coatings.
  • a conveyability improved in this way results in a greatly simplified feeding in of the powdered coating material and a dramatic reduction in the outlay on equipment.
  • Methods according to the invention which can be used to build up coatings are for example cold gas spraying, thermal plasma spraying, non-thermal plasma spraying, flame spraying and high-speed flame spraying.
  • An improved conveyability has proved to be of particularly great importance in particular in coating methods in which as low as possible a thermal load of the substrate is to be effected and no, or almost no, thermal component is used to apply the coating.
  • the use of the powdered coating material according to the invention in flame spraying, non-thermal plasma spraying, cold gas spraying and high-speed flame spraying is preferred.
  • 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 guarantee a continuous operation, the storage of large amounts of the gas used.
  • combustible gases are necessary to generate the flame in flame spraying, their storage is associated with a corresponding safety risk and therefore requires special safety regulations.
  • a plasma in contrast, can also be produced using non-combustible gases, with the result that the storage of corresponding amounts of gas is associated with lower safety standards and therefore reduced costs.
  • non-thermal plasma spraying is used as coating method.
  • additive within the meaning of the present invention relates to substances which are present, not cross-linked, i.e. they have not been cross-linked, on the surface of the particles of the powdered coating material.
  • additive relates, in preferred embodiments of the present invention, to carbon-containing compounds which have not been cross-linked on the surface of the particles of the powdered coating material.
  • not cross-linked on the surface is meant that no covalent bonds between the individual additive molecules are built up during or after the application of the additive to the particles of the powdered coating material, consequently no post-cross-linking takes place on the pigment surface.
  • additive is not meant cross-linked polymers such as are disclosed for example in EP 2115075 A1.
  • the additives are only bound to the particles of the powdered coating material by means of physical bonds, for example by means of van der Waals interactions, dipole-dipole interactions or hydrogen bridges.
  • the additives are additionally or alternatively bound to the surface of the particles of the powdered coating material by means of chemical bonds, such as for example covalent or ionic bonds.
  • the additives according to the invention can be removed from the particles again through the use of organic and/or aqueous solvents.
  • Such additives have in particular the advantage that they are easy and inexpensive to apply.
  • particular preferred additives can be dispersed for example in a solvent and applied to the powder particles by mechanical forces.
  • the additives can be dissolved in a suitable solvent, then mixed with the powder particles and applied by evaporation of the solvent onto the powder particles.
  • the inventors are of the view that the additives according to the invention reduce the interactions between the particles and thereby increase the conveyability.
  • Substances which as additives within the meaning of the present invention are in particular carbon-containing compounds which are chemically and/or physically bound to the surface of the particles of the powdered coating material.
  • the inventors are of the view that a particularly strong improvement in the coatings produced according to the invention is brought about in the use of additives with a high carbon content in a combustion flame or a plasma flame by combusting the additive in the flame and applying agglomerates of the powdered coating material present here.
  • the weight proportion of the carbon atoms in the additive-covered powdered coating material is at least 0.01 wt.-%, preferably at least 0.05 wt.-%, more preferably at least 0.1 wt.-% and still more preferably at least 0.17 wt.-%.
  • the weight proportion of the carbon atoms in the additive-covered powdered coating material is at least 0.22 wt.-%, preferably at least 0.28 wt.-%, more preferably at least 0.34 wt.-% and still more preferably at least 0.4 wt.-%.
  • the above-named wt.-% are based on the total weight of the coating material and the additive.
  • the weight proportion of the carbon atoms in the additive-covered powdered coating material is at most 15 wt.-%, preferably at most 10 wt.-%, more preferably at most 7 wt.-% and still more preferably at most 5 wt.-%.
  • the carbon content is at most 4 wt.-%, preferably at most 3 wt.-%, more preferably at most 2 wt.-% and still more preferably at most 1 wt.-%.
  • the above-named wt.-% are based on the total weight of the coating material and the additive.
  • the weight proportion of the carbon atoms in the additive-covered powdered coating material lies in the range of between 0.01 wt.-% and 15 wt.-%, preferably in the range of between 0.05 wt.-% and 10 wt.-%, more preferably in the range of between 0.1 wt.-% and 7 wt.-% and still more preferably in the range of between 0.17 wt.-% and 5 wt.-%.
  • the weight proportion of the carbon atoms in the additive-covered powdered coating material lies in the range of between 0.22 wt.-% and 4 wt.-%, preferably in the range of between 0.28 wt.-% and 3 wt.-%, more preferably in the range of between 0.34 wt.-% and 2 wt.-% and still more preferably in the range of between 0.4 wt.-% and 1 wt.-%.
  • the above-named wt.-% are based on the total weight of the coating material and the additive.
  • the weight proportion of the carbon atoms to the total weight of the coating material and the additive is determined for example with a CS 200 device from Leco Instruments GmbH.
  • the compounds used as additive contain at least 6 carbon atoms, preferably at least 7 carbon atoms, more preferably at least 8 carbon atoms and still more preferably at least 9 carbon atoms.
  • the compounds used as additive contain at least 10 carbon atoms, preferably at least 11 carbon atoms, more preferably at least 12 carbon atoms and still 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 respective additive. All methods known to a person skilled in the art for determining a substance can be used here.
  • an additive can be removed from the particles of the powdered coating material using organic and/or aqueous solvents and then identified by means of HPLC, GCMS, NMR, CHN or combinations of the above-named with each other or with other routinely used methods.
  • the weight proportion of the additive, or additives is at least 0.02 wt.-%, preferably at least 0.08 wt.-%, more preferably at least 0.17 wt.-% and still more preferably at least 0.30 wt.-%.
  • the C content of the coating material and the additive is at least 0.35 wt.-%, preferably at least 0.42 wt.-%, more preferably at least 0.54 wt.-% and still more preferably at least 0.62 wt.-%.
  • the above-named wt.-% are based on the total weight of the coating material and the additive.
  • the weight proportion of the additive is at most 32 wt.-%, preferably at most 18 wt.-%, more preferably at most 13 wt.-% and still more preferably at most 9 wt.-%.
  • the C content of the coating material and the additive is at most 7 wt.-%, preferably at most 6 wt.-%, more preferably at most 4.5 wt.-% and still more preferably at most 2.3 wt.-%.
  • the above-named wt.-% are based on the total weight of the coating material and the additive.
  • the weight proportion of the additive lies in the range of between 0.02 wt.-% and 32 wt.-%, preferably in the range of between 0.08 wt.-% and 18 wt.-%, more preferably in the range of between 0.17 wt.-% and 13 wt.-% and still more preferably in the range of between 0.30 wt.-% and 9 wt.-%.
  • polymers e.g. polysaccharides, plastics
  • monomers silanes, waxes, oxidized waxes, carboxylic acids (e.g. fatty acids), phosphonic acids, derivatives of the above-named (in particular carboxylic acid derivatives and phosphoric acid derivatives) and mixtures thereof.
  • polysaccharides, plastics, silanes, waxes, oxidized waxes, carboxylic acids (e.g. fatty acids) carboxylic acid derivatives, phosphonic acids, phosphoric acid derivatives or mixtures thereof preferably polysaccharides, silanes, waxes, oxidized waxes, carboxylic acids (e.g.
  • 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, are used as additive.
  • the above-named waxes comprise both natural waxes and synthetic waxes.
  • waxes are paraffin waxes, petroleum waxes, montan waxes, animal waxes (e.g. beeswax, shellac, wool wax), vegetable waxes (e.g. carnauba wax, candelilla wax, rice bran wax), fatty acid amide waxes (such as e.g. erucamide), polyolefin waxes (such as e.g. polyethylene waxes, polypropylene waxes), grafted polyolefin waxes, Fischer-Tropsch waxes, and oxidized polyethylene waxes and modified polyethylene and polypropylene waxes (e.g.
  • waxes according to the invention are preferably bound via physical bonds in particular embodiments. However, it is not ruled out that in further particular embodiments the waxes have functional groups which alternatively or additionally make an ionic and/or covalent bond possible.
  • polymer within the meaning of the present invention also comprises oligomers.
  • the polymers used according to the invention are, however, preferably built up of at least 25 monomer units, more preferably of at least 35 monomer units, still more preferably of at least 45 monomer units and most preferably of at least 50 monomer units.
  • the polymers can be bound here to the particles of the powdered coating material without covalent or ionic bonds being formed.
  • the additive according to the invention can form at least one ionic or covalent bond with the particles of the powdered coating material.
  • such a binding preferably takes place via a phosphoric acid, carboxylic acid, silane or sulfonic acid group contained in the polymer.
  • polysaccharide within the meaning of the present invention also comprises oligosaccharides.
  • the polysaccharides used according to the invention are, however, preferably built up of at least 4 monomer units, more preferably of at least 8 monomer units, still more preferably of at least 10 monomer units and most preferably of at least 12 monomer units.
  • particularly preferred polysaccharides are cellulose, cellulose derivatives such as e.g. methyl cellulose, ethyl cellulose, carboxymethyl celluose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, nitrocellulose (e.g.
  • cellulose esters e.g. cellulose acetate, cellulose acetobutyrate, and cellulose propionate
  • starches such as e.g. corn starch, potato starch and wheat starch and modified starches.
  • Thermoplastic plastics are particularly preferred here, wherein all thermoplastics known to a person skilled in the art come into consideration.
  • a summary of corresponding thermoplastics is found e.g. in the Kunststoff-Taschenbuch, ed. Saechtling, 25th edition, Hanser-Verlag, Kunststoff, 1992, in particular chapter 4, as well as references cited therein, and in the Kunststoff-Handbuch, ed. G. Becker and D. Braun, volumes 1 to 11 , Hanser-Verlag, Kunststoff, 1966 to 1996.
  • thermoplastics are to be named by way of example for illustration: 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 HIPS, or ASA, ABS or AES polymers, polyarylene ethers such as polyphenylene ether (PPE), polysulfones, polyurethanes, polylactides, halogen-containing polymers, polymers containing imide groups, cellulose esters, silicone polymers and thermoplastic elastomers.
  • PC polycarbonates
  • PET polyethylene terephthalate
  • PP polypropylene
  • PP poly(meth)acrylates
  • polyamides vinylaromatic (co)polymers
  • Polyoxyalkylene homo- or copolymers in particular (co)polyoxymethylenes (POM), and methods for the production thereof are known per se to a person skilled in the art and described in the literature.
  • the polymer main chain of these polymers has at least 50 mol.-% recurring units of —CH 2 O—.
  • the homopolymers are generally produced, preferably catalytically, by polymerization of formaldehyde or trioxane.
  • Polyoxymethylene copolymers and polyoxymethylene terpolymers are examples.
  • Suitable polycarbonates are known per se and can be obtained e.g. according to DE 1 300 266 B1 by means of interfacial polycondensation or according to DE 14 95 730 A1 by reacting biphenyl carbonate with bisphenols.
  • polyesters are also known per se and described in the literature.
  • the polyesters can be produced by reacting aromatic dicarboxylic acids, esters thereof or other ester-forming derivatives of same with aliphatic dihydroxy compounds in a manner known per se.
  • naphthalene dicarboxylic acid, terephthalic acid and isophthalic acid or mixtures thereof are used as dicarboxylic acids.
  • 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, dodecane diacids and cyclohexane dicarboxylic acids.
  • aliphatic dihydroxy compounds are diols with 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 are polyethylene and polypropylene as well as copolymers based on ethylene or propylene, optionally also with higher ⁇ -olefins.
  • polyolefin within the meaning of the present invention also comprises ethylene-propylene elastomers and ethylene-propylene terpolymers.
  • poly(meth)acrylates examples include polymethyl methacrylate (PMMA) and copolymers based on methyl methacrylate with up to 40 wt.-% further copolymerizable monomers, such as e.g. n-butyl acrylate, t-butyl acrylate or 2-ethylhexyl acrylate.
  • PMMA polymethyl methacrylate
  • copolymers based on methyl methacrylate with up to 40 wt.-% further copolymerizable monomers such as e.g. n-butyl acrylate, t-butyl acrylate or 2-ethylhexyl acrylate.
  • polyamides also comprise polyetheramides such as polyether block amides and are described for example in the disclosures of U.S. Pat. No. 2,071,250, U.S. Pat. No. 2,071,251, U.S. Pat. No. 2,130,523, U.S. Pat. No. 2,130,948, U.S. Pat. No. 2,241,322, U.S. Pat. No. 2,312,966, U.S. Pat. No. 2,512,606 and U.S. Pat. No. 3,393,210.
  • polyamides comprise for example polycaprolactams, polycapryllactams, polylaurolactams and polyamides, which are obtained by reacting dicarboxylic acids with diamines.
  • dicarboxylic acids suitable for this are alkanedicarboxylic acids with 6 to 12, in particular 6 to 10 carbon atoms and aromatic dicarboxylic acids can be used.
  • suitable diamines are alkanediamines with 6 to 12, in particular 6 to 8 carbon atoms, as well as 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-acrytnitrile copolymers
  • HIPS High Impact Polystyrene
  • ASA acrylonitrile-styrene-acrylester
  • ABS acrylonitrile-butadiene-styrene
  • AES acrylonitrile-EPDM rubber-styrene
  • ABS polymers are found for example in DE 197 28 629 A1 and the production of ASA polymers is found for example in EP 99 532 A2. Details on the production of AES polymers is furthermore found for example in U.S. Pat. No. 3,055,859 or in U.S. Pat. No. 4,224,419.
  • polyarylene ethers examples include polyarylene ethers per se, polyarylene ether sulfides, polyarylene ether sulfones and polyarylene ether ketones.
  • the arylene groups thereof can be the same or different, and independently of each other can be for example an aromatic radical with 6 to 18 C atoms.
  • suitable arylene radicals are phenylene, bisphenylene, terphenylene, 1,5-naphthylene, 1,6-naphthylene, 1,5-anthrylene, 9,10-anthrylene or 2,6-anthrylene.
  • Examples of production details for polyarylene ether sulfones are found in EP 113 112 A1 and EP 135 130 A2.
  • polymers of lactic acid, polylactides, as well as methods for the production thereof are known to a person skilled in the art.
  • copolymers or block copolymers based on lactic acid and further monomers it is preferred in particular to use copolymers or block copolymers based on lactic acid and further monomers.
  • halogen-containing polymers are polymers of vinyl chloride, such as polyvinyl chloride (PVC) (e.g. hard PVC and soft 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 fluor
  • polyimides examples include polyimides, polyetherimides, and polyamide-imides.
  • polyimides examples include polyimides, polyetherimides, and polyamide-imides.
  • Such polymers are described for example in Römpp Chemie Lexikon, CD-ROM version 1.0, Thieme Verlag Stuttgart 1995.
  • thermoplastic elastomers are characterized in that they can be processed like thermoplastics but have rubber-elastic properties. More detailed information is found for example in G. Holden et al., Thermoplastic Elastomers, 2nd edition, Hanser Verlag, Kunststoff 1996.
  • thermoplastic polyurethane elastomers TPE-U or TPU
  • styrene oligoblock copolymers TPE-S
  • SBS styrene-butadiene-styrene-o ⁇ y block copolymer
  • SEES styrene-ethylene-butylene-styrene block copolymer, obtainable by hydrogenation of SBS
  • thermoplastic polyolefin elastomers TPE-O
  • thermoplastic polyester elastomers TPE-E
  • thermoplastic polyamide elastomers TPE-A
  • thermoplastic vulcanisates TPE-V
  • polyacrylates examples are 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 are selected from the group consisting of the products of the copolymerization of PE or PP with maleic acid (anhydride) or acrylic acid.
  • the polymers used as additives have a molecular weight of at most 200,000, preferably of at most 170,000, more preferably of at most 150,000 and still more preferably at most 130,000.
  • the compounds used as additives have a molecular weight of at most 110,000, preferably of at most 90,000, more preferably of at most 70,000 and still more preferably of at most 50,000.
  • carboxylic acids also comprise in particular dicarboxylic acids, tricarboxylic acids and tetracarboxylic acids in particular embodiments.
  • dicarboxylic acids are succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
  • the above-named carboxylic acid derivatives are directed in particular towards carboxylic acid esters.
  • fatty acids examples include capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, undecylenic acid, palmitoleic acid, elaidic acid, vaccenic acid, eicosenoic acid, cetoleic acid, erucic acid, nervonic acid, sorbic acid, linoleic acid, linolenic acid, eleostearic acid, arachidonic acid, timnodonic acid, clupanodonic acid, docosahexaenoic acid, stearic acid and oleic acid.
  • the additives comprise no stearic acid or oleic acid and preferably no saturated or unsaturated C18 carboxylic acids, more preferably no saturated or unsaturated C14 to C18 carboxylic acids, still more preferably no saturated or unsaturated C12 to C18 carboxylic acids and most preferably no saturated or unsaturated C10 to C20 carboxylic acids.
  • C followed by a number relates within the meaning of the present invention to the carbon atoms contained in a molecule or molecule constituent, wherein the number expresses the quantity of carbon atoms.
  • X can be the same or different and is hydrogen, hydroxy, halogen or —NR′ 2
  • R′ can be the same or different and is hydrogen, a substituted or unsubstituted C1-C9 alkyl group or a substituted or unsubstituted aryl group
  • Y can be the same or different and is —O—, —S—, —NH— or —NR— and R can be the same or different and is selected from the group consisting of C1-C30 alkyl groups, C2-C30 alkenyl groups, C2-C30 alkinyl groups, C5-C30 aryl groups, C6-C30 arylalkyl groups, C4-C30 heteroaryl groups, C5-C30 heteroarylalkyl groups, C3-C30 cycloalkyl groups, C4-C30 cycloalkylalkyl groups, C2-C30 heterocycloalkyl groups, C2-C30 heterocycloalkyl groups, C2-C
  • substituted within the meaning of the present invention describes that at least one hydrogen atom of the relevant group by a halogen, hydroxy, cyano, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkinyl, C1-C5 alkanoyl, C3-C8 cycloalkyl, heterocyclic, aryl, heteroaryl, C1-C7 alkylcarbonyl, C1-C7 alkoxy, C2-C7 alkenyloxy, C2-C7 alkinyloxy, aryloxy, acyl, C1-C7 acryloxy, C1-C7 methacryloxy, C1-C7 epoxy, C1-C7 vinyl, C1-C5 alkoxycarbonyl, aroyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, amincarbonyloxy, C1-C7 alkylaminocarbonyloxy, C1-C7 dial
  • cycloalkyl group and “heterocycloalkyl group” within the meaning of the present invention comprise saturated, partially saturated and unsaturated systems, apart from aromatic systems, which are called “aryl groups” or “heteroaryl groups”.
  • alkyl within the meaning of the present invention, unless otherwise indicated, preferably represents straight or branched C1 to C27, more preferably straight or branched C1 to C25 and still more preferably straight or branched C1 to C20 carbon chains.
  • alkenyl and alkinyl within the meaning of the present invention, unless otherwise indicated, preferably represent straight or branched C2 to C27, more preferably straight or branched C2 to C25 and still more preferably straight or branched C2 to C20 carbon chains.
  • aryl within the meaning of the present invention represents aromatic carbon rings, preferably aromatic carbon rings with at most 7 carbon atoms, more preferably the phenyl ring, wherein the above-named aromatic carbon rings can be a constituent of a condensed ring system.
  • aryl groups are phenyl, hydroxyphenyl, biphenyl and naphthyl.
  • heteroaryl within the meaning of the present invention represents aromatic rings, in which a carbon atom of an analogous aryl ring has formally been replaced by a heteroatom, preferably by an atom selected from the group consisting of O, S and N.
  • silanes are characterized by a structure according to Formula (II):
  • X can be the same or different and is hydrogen, hydroxy, halogen or —NR′ 2
  • R′ can be the same or different and is hydrogen, a substituted or unsubstituted C1-C9 alkyl group or a substituted or unsubstituted aryl group and R can be the same or different and is selected from the group consisting of C1-C30 alkyl groups, C2-C30 alkenyl groups, C2-C30 alkinyl groups, C5-C30 aryl groups, C6-C30 arylalkyl groups, C4-C30 heteroaryl groups, C5-C30 heteroarylalkyl groups, C3-C30 cycloalkyl groups, C4-C30 cycloalkylalkyl groups, C2-C30 heterocycloalkyl groups, C3-C30 heterocycloalkylalkyl groups, C1-C30 ester groups, C1-C30 alkyl ether groups,
  • the additive can be bound for example chemically or physically to the surface of the particles of the powdered coating material. It is not necessary here that an unbroken surface coverage of the particles is carried out, even if this is preferred in particular embodiments of the present invention.
  • the additives are bound as weakly as possible to the surface of the particles of the powdered coating material.
  • the additives used according to the invention carry no functional groups.
  • the term “functional group” within the meaning of the present invention denotes molecular groups in molecules which decisively influence the substance 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 cannot be removed from the surface too easily, for example as a result of friction.
  • 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 the powdered coating materials covered with an additive according to the invention are used, the use of coating materials with an unexpectedly high melting point also allowed.
  • the inventors are of the view that the more uniform conveying of the particles with reduced tendency to agglomerate allows the particles to strike the substrate surface individually and the kinetic energy present to be able to be utilized fully to shape the particle.
  • some of the kinetic energy is apparently used up by the breakup of the agglomerate and particles that strike later are cushioned by coating material already present at this site, but not yet solidified. If the powdered coating material is passed through a flame beforehand, the thermal energy is furthermore probably better transferred to the particles in the case of uniformly fed-in particles without agglomerates.
  • powdered coating materials covered with at least one additive can also be used to produce homogeneous layers if the melting point, measured in [K], of the coating material 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 method directed onto the substrate, for example the gas stream, the combustion flame and/or the plasma flame.
  • powdered coating materials covered with at least one additive can also be used to produce homogeneous layers if the melting point, measured in [K], of the coating material is up to 75%, preferably up to 80%, more preferably up to 85% and still more preferably up to 90% of the temperature, measured in [K], of the medium used in the coating method directed onto the substrate, for example the gas stream, the combustion flame and/or the plasma flame.
  • the above-named percentages relate 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” within the meaning of the present invention describes that the relevant coating has less than 10%, preferably less than 5%, more preferably less than 3%, still more preferably less than 1% and most preferably less than 0.1% cavities. In particular, it is preferred that no cavities at all are recognizable.
  • the above-named term “cavity” within the meaning of the present invention describes the proportion of holes, incorporated in the coating, on the two-dimensional surface of a cross-section of the coated substrate, relative to the coating contained in the two-dimensional surface. A determination of this proportion is carried out by means of SEM at 30 randomly selected sites on the coating produced according to the invention, wherein for example a length of 100 ⁇ m of the substrate coating is examined.
  • the size distribution of the particles is preferably determined 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 computationally 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.
  • the size distribution is determined, calculated in the form of a volume average relative to the equivalent spherical diameter.
  • This volume-averaged size distribution can be represented as a cumulative frequency distribution.
  • the cumulative frequency distribution is characterized in a simplified manner by different characteristic values, for example the D 10 , D 50 or D 90 value.
  • the measurements can be carried out for example with the particle-size analyzer HELOS from Sympatec GmbH, Clausthal-Zellerfeld, Germany.
  • a dry powder can be dispersed using a dispersing unit of the Rodos T4.1 type at a primary pressure of for example 4 bar.
  • a size distribution curve of the particles can be measured, for example, with a device from Quantachrome (device: Cilas 1064) according to the manufacturer's instructions. For this, 1.5 g of the powdered coating material is suspended in approx.
  • the powdered 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 still more preferably at most 49 ⁇ m.
  • the powdered 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 still more preferably at most 45 ⁇ m.
  • D 50 within the meaning of the present invention denotes the particle size at which 50% of the above-named particle-size distribution volume-averaged by means of laser granulometry lies below the indicated value.
  • the measurements can be carried out for example according to the above-named measurement method with 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 still more preferably at least 6 ⁇ m.
  • the powdered 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 still more preferably at least 13 ⁇ m.
  • the powder has a particle-size distribution with a D 50 value in the range of from 1.5 to 53 ⁇ m, preferably in the range of from 2 to 51 ⁇ m, more preferably in the range of from 4 to 50 ⁇ m and still more preferably in the range of from 6 to 49 ⁇ m.
  • the powder has a particle-size distribution with a D 50 value in the range of from 7 to 48 ⁇ m, preferably in the range of from 9 to 47 ⁇ m, more preferably in the range of from 11 to 46 ⁇ m and still more preferably in the range of from 13 to 45 ⁇ m.
  • the powder has a particle-size distribution with a D 50 value in the range of from 1.5 to 45 ⁇ m, preferably in the range of from 2 to 43 ⁇ m, more preferably in the range of from 2.5 to 41 ⁇ m and still more preferably in the range of from 3 to 40 ⁇ m.
  • the powder has a particle-size distribution with a D 50 value in the range of from 3.5 to 38 ⁇ m, preferably in the range of from 4 to 36 ⁇ m, more preferably in the range of from 4.5 to 34 ⁇ m and still more preferably in the range of from 5 to 32 ⁇ m.
  • the powder has a particle-size distribution with a D 50 value in the range of from 9 to 53 ⁇ m, preferably in the range of from 12 to 51 ⁇ m, more preferably in the range of from 15 to 50 ⁇ m, still more preferably in the range of from 17 to 49 ⁇ m.
  • the powder has a particle-size distribution with a D 50 value in the range of from 19 to 48 ⁇ m, preferably in the range of from 21 to 47 ⁇ m, more preferably in the range of from 23 to 46 ⁇ m and still more preferably in the range of from 25 to 45 ⁇ m.
  • the powdered 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, still more preferably at most 91 ⁇ m and most preferably at most 87 ⁇ m.
  • the powdered 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 within the meaning of the present invention denotes the particle size at which 90% of the above-named particle-size distribution volume-averaged by means of laser granulometry lies below the indicated value.
  • the measurements can be carried out for example according to the above-named measurement method with a particle-size analyzer HELOS from Sympatec GmbH, Clausthal-Zellerfeld, Germany.
  • the powdered 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 still more preferably at least 15 ⁇ m.
  • the powdered coating material has a particle-size distribution with a D 90 value of at least 17 ⁇ m, preferably at least 19 ⁇ m, more preferably at least 21 ⁇ m and still more preferably at least 22 ⁇ m.
  • the powdered coating materials have a particle-size distribution with a D 90 value in the range of from 42 to 103 ⁇ m, preferably in the range of from 45 to 99 ⁇ m, more preferably in the range of from 48 to 95 ⁇ m and still more preferably in the range of from 50 to 91 ⁇ m.
  • the powdered coating material has a D 90 value in the range of from 52 to 87 ⁇ m, preferably in the range of from 54 to 81 ⁇ m, more preferably in the range of from 56 to 75 ⁇ m and still more preferably in the range of from 57 to 71 ⁇ m.
  • the powdered 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 still more preferably at most 2.5 ⁇ m.
  • the powdered coating material has a particle-size distribution with 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.
  • D 10 within the meaning of the present invention denotes the particle size at which 10% of the above-named particle-size distribution volume-averaged by means of laser granulometry lies below the indicated value.
  • the measurements can be carried out for example according to the above-named measurement method with a particle-size analyzer HELOS from Sympatec GmbH, Clausthal-Zellerfeld, Germany.
  • the additive-covered powdered coating materials with a high fines proportion also still have a strong tendency to form fine dusts, which makes the handling of corresponding powders much more difficult.
  • the additive-covered, powdered 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 still more preferably at least 0.6 ⁇ m.
  • the additive-covered, powdered 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 still more preferably at least 1.0 ⁇ m.
  • the additive-covered, powdered coating material is characterized in that it have a particle-size distribution with a D 10 value from a range of from 0.2 to 5 ⁇ m, preferably from a range of from 0.4 to 4 ⁇ m, more preferably from a range of from 0.5 to 3 ⁇ m and still more preferably from a range of from 0.6 to 2.5 ⁇ m.
  • the additive-covered, powdered coating material has a particle-size distribution with a D 10 value from a range of from 0.7 to 2.2 ⁇ m, preferably from a range of from 0.8 to 2.1 ⁇ m, more preferably from a range of from 0.9 to 2.0 ⁇ m and still more preferably from a range of from 1.0 to 1.9 ⁇ m.
  • the powdered coating material has a particle-size distribution with a D 10 value of from 3.7 to 26 ⁇ m, a D 50 value of from 6 to 49 ⁇ m and a D 90 value of from 12 to 86 ⁇ m.
  • the powdered coating material has a particle-size distribution with a D 10 value of from 5.8 to 26 ⁇ m, a D 50 value of from 11 to 46 ⁇ m and a D 90 value of from 16 to 83 ⁇ m.
  • the powdered coating material has a particle-size distribution with a D 10 value of from 9 to 19 ⁇ m, a D 50 value of from 16 to 35 ⁇ m and a D 90 value of from 23 to 72 ⁇ m.
  • the powdered coating material has a particle-size distribution with a D 10 value of from 0.8 to 28 ⁇ m, a D 50 value of from 1.5 to 45 ⁇ m and a D 90 value of from 2.5 to 81 ⁇ m.
  • the powdered coating material has a particle-size distribution with a D 10 value of from 2.2 to 22 ⁇ m, a D 50 value of from 4 to 36 ⁇ m and a D 90 value of from 4 to 62 ⁇ m.
  • the powdered coating material has a particle-size distribution with a D 10 value of from 2.8 to 17 ⁇ m, a D 50 value of from 6 to 28 ⁇ m and a D 90 value of from 9 to 49 ⁇ m.
  • the powdered coating material has a particle-size distribution with a D 10 value of from 4.8 to 29 ⁇ m, a D 50 value of from 9 to 53 ⁇ m and a D 90 value of from 13 to 97 ⁇ m.
  • the powdered coating material has a particle-size distribution with a D 10 value of from 12 to 26 ⁇ m, a D 50 value of from 23 to 46 ⁇ m and a D 90 value of from 35 to 87 ⁇ m.
  • the powdered coating material has a particle-size distribution with a D 10 value of from 15 to 24 ⁇ m, a D 50 value of from 28 to 44 ⁇ m and a D 90 value of from 41 to 78 ⁇ m.
  • the inventors have found that in particular embodiments, for example, a still more uniform conveyability of the powdered coating material is achieved through the use of a powdered coating material with a smaller span, which further simplifies the formation of a more homogeneous and higher-quality layer.
  • the span of the powdered coating material is at most 2.9, preferably at most 2.6, more preferably at most 2.4 and still more preferably at most 2.1.
  • the span of the powdered coating material is at most 1.9, preferably at most 1.8, more preferably at most 1.7 and still more preferably at most 1.6.
  • the span value of the powdered coating material is at least 0.4, preferably at least 0.5, more preferably at least 0.6 and still more preferably at least 0.7. In particular embodiments, it is preferred in particular that 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 still more preferably at least 1.1.
  • the powdered coating material has a span value in the range of from 0.4 to 2.9, preferably in the range of from 0.5 to 2.6, more preferably in the range of from 0.6 to 2.4 and still more preferably in the range of from 0.7 to 2.1.
  • the powdered coating material has a span value in the range of from 0.8 to 1.9, preferably in the range of from 0.9 to 1.8, more preferably in the range of from 1.0 to 1.7 and still more preferably in the range of from 1.1 to 1.6.
  • the powdered coating material has a particle-size distribution with a span in the range of from 0.4 to 2.9 and a D 50 value in the range of from 1.5 to 53 ⁇ m, preferably in the range of from 2 to 51 ⁇ m, more preferably in the range of from 4 to 50 ⁇ m, still more preferably in the range of from 6 to 49 ⁇ m and most preferably in the range of from 7 to 48 ⁇ m.
  • the powdered coating material has a particle-size distribution with a span in the range of from 0.5 to 2.6 and a D 50 value in the range of from 1.5 to 53 ⁇ m, preferably in the range of from 2 to 51 ⁇ m, more preferably in the range of from 4 to 50 ⁇ m, still more preferably in the range of from 6 to 49 ⁇ m and most preferably in the range of from 7 to 48 ⁇ m.
  • the powdered coating material has a particle-size distribution with a span in the range of from 0.6 to 2.4 and a D 50 value in the range of from 1.5 to 53 ⁇ m, preferably in the range of from 2 to 51 ⁇ m, more preferably in the range of from 4 to 50 ⁇ m, still more preferably in the range of from 6 to 49 ⁇ m and most preferably in the range of from 7 to 48 ⁇ m.
  • the powdered coating material has a particle-size distribution with a span in the range of from 0.7 to 2.1 and a D 50 value in the range of from 1.5 to 53 ⁇ m, preferably in the range of from 2 to 51 ⁇ m, more preferably in the range of from 4 to 50 ⁇ m, still more preferably in the range of from 6 to 49 ⁇ m and most preferably in the range of from 7 to 48 ⁇ m.
  • the density of the powdered coating material can influence the conveying of such powders in the form of an aerosol.
  • the inventors are of the view that the differences in inertia of particles that are the same size but have different densities lead to a different behavior of the aerosol streams of powdered coating materials with identical particle-size distribution. It can therefore prove to be difficult to transfer conveying methods which have been optimized for a specific D 50 to powdered coating materials with other densities. In particular embodiments, therefore, it is preferred that the upper limit of the span value is corrected dependent on the density of the powdered coating material used.
  • Span UC Span U ⁇ ( ⁇ Alu ⁇ X ) 1 3
  • Span UC is the corrected upper span value
  • Span O is the upper span value
  • p Alu is the density of aluminum (2.7 g/cm 3 )
  • ⁇ X is the density of the powdered coating material used.
  • a powdered coating material with an uncorrected upper span value is therefore used for powdered coating materials with a density lower than the density of aluminum.
  • Coating methods that can be used according to the invention are known to a person skilled in the art under the names cold gas spraying, thermal plasma spraying, non-thermal plasma spraying, flame spraying and high-speed flame spraying.
  • Cold gas spraying is characterized in that the powder to be applied is not melted in the gas jet, but the particles are greatly accelerated and, as a result of their kinetic energy, form a coating on the surface of the substrate.
  • various gases known to a person skilled in the art can be used as carrier gas, such as nitrogen, helium, argon, air, krypton, neon, xenon, carbon dioxide, oxygen or mixtures thereof.
  • Gas speeds of up to 3000 m/s are achieved through a controlled expansion of the above-named gases in a corresponding nozzle.
  • the particles can be accelerated here to up to 2000 m/s.
  • a disadvantage is, for example, the strong generation of noise which is brought about by the high speeds of the gas streams used.
  • a powder is converted to the liquid or plastic state by means of a flame and then applied to a substrate as coating.
  • a substrate e.g. a mixture of oxygen and a combustible gas such as acetylene or hydrogen is combusted.
  • some of the oxygen is used to transport the powdered coating material into the combustion flame. The particles achieve speeds of between 24 and 31 m/s in customary variants of this method.
  • a powder is also converted to a liquid or plastic state by means of a flame.
  • the particles are accelerated to significantly higher speeds compared with the above-named method.
  • a speed of the gas stream of from 1220 to 1525 m/s with a speed of the particles of from approx. 550 to 795 m/s is named.
  • gas speeds of over 2000 m/s are also achieved.
  • it is preferred that the speed of the flame lies between 1000 and 2500 m/s.
  • the flame temperature lies between 2200° C. and 3000° C.
  • the temperature of the flame is thus comparable to the temperature in flame spraying. This is achieved by combusting the gases under a pressure of from approx. 515 to 621 kPa, followed by expansion of the combustion gases in a nozzle.
  • the view is taken that coatings produced here have a higher density than, for example, coatings obtained by the flame spraying method.
  • Detonation/explosive flame spraying can be viewed as a subtype of high-speed flame spraying.
  • the powdered coating material is strongly accelerated by repeated detonations of a gas mixture such as acetylene/oxygen, wherein for example particle speeds of approx. 730 m/s are achieved.
  • the detonation frequency of the method lies for example between approx. 4 and 10 Hz.
  • detonation frequencies of around approx. 100 Hz are also chosen.
  • the layers obtained are usually supposed to have a particularly high hardness, strength, density and good binding to the substrate surface.
  • a disadvantage in the above-named methods is the increased safety costs, as well as for example the high noise load because of the high gas speeds.
  • thermal plasma spraying for example, a direct current arc furnace is passed through by a primary gas such as argon at a speed of 40 l/min and a secondary gas such as hydrogen at a speed of 2.5 l/min, wherein a thermal plasma is generated. Then, for example, 40 g/min of the powdered coating material is fed in with the aid of a carrier gas stream, which is passed into the plasma flame at a speed of 4 l/min.
  • the conveying 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 whole gas stream is furthermore preferably 30 to 150 SLPM (standard liters per minute) in particular variants.
  • the electrical power used to ionize the gas stream, 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.
  • plasma temperatures of between 4000 K and a few 10000 K can be achieved.
  • a non-thermal plasma is used to activate the powdered coating material.
  • the plasma used here is generated for example with a barrier discharge or corona discharge with a frequency of from 50 Hz to 1 MHz. In particular variants of non-thermal plasma spraying, it is preferred that work is done at a frequency of from 10 kHz to 100 kHz.
  • the temperature of the plasma here is preferably less than 3000 K, preferably less than 2500 K and still more preferably less than 2000 K. This minimizes the technical outlay and keeps the input of energy into the coating material to be applied as low as possible, which in turn allows a gentle coating of the substrate.
  • Non-thermal plasmas the core temperature of which is below 1173 K or even below 773 K in the core region can also be generated by targeted choice of the parameters.
  • the temperature in the core region is measured here, for example, using an NiCr/Ni thermocouple and a spray diameter of 3 mm at a distance of 10 mm from the nozzle outlet in the core of the emerging plasma jet at ambient pressure.
  • Such non-thermal plasmas are suitable in particular for coatings of very temperature-sensitive substrates.
  • the outlet opening for the plasma flame such that the track widths of the coatings produced lie between 0.2 mm and 10 mm.
  • a distance of 1 mm is chosen as the distance from the spray lance to the substrate. This makes possible as great a flexibility as possible of the coatings and, at the same time, guarantees high-quality coatings.
  • the distance between spray lance and substrate expediently lies between 1 mm and 35 mm.
  • ionizable gas in the non-thermal plasma method.
  • gases known to a person skilled in the art and mixtures thereof can be used as ionizable gas in the non-thermal plasma method.
  • gases known to a person skilled in the art and mixtures thereof can be used as ionizable gas in the non-thermal plasma method.
  • gases 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 stream lies below 200 m/s.
  • a value of between 0.01 m/s and 100 m/s, preferably between 0.2 m/s and 10 m/s, can be chosen as the flow rate.
  • the volume flow of the carrier gas lies between 10 and 25 l/min, more preferably between 15 and 19 l/min.
  • the particles of the powdered coating material are preferably metallic particles or metal-containing particles. It is preferred in particular that the metal content of the metallic particles or metal-containing particles is at least 95 wt.-%, preferably at least 99 wt.-%, still more preferably at least 99.9 wt.-%.
  • the metal is, or the 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 is, or the metals are, 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 powdered coating material is or are selected from the group consisting of silver, aluminum, zinc, tin, copper, alloys and mixtures thereof.
  • metallic particles or metal-containing particles in which the metal is, or the metals are, selected from the group consisting of silver, aluminum and tin have proved to be particularly suitable particles in specific embodiments.
  • the powdered coating material consists of inorganic particles which are preferably selected from the group consisting of carbonates, oxides, hydroxides, carbides, halides, nitrides and mixtures thereof. Mineral and/or metal-oxide particles are particularly suitable.
  • the inorganic particles are alternatively or additionally selected from the group consisting of carbonaceous particles or graphite particles.
  • a further possibility is the use of mixtures of the metallic particles and the above-named inorganic particles, such as for example mineral and/or metal-oxide particles, and/or the particles which are selected from the group consisting of carbonates, oxides, hydroxides, carbides, halides, nitrides and mixtures thereof.
  • the powdered coating material can comprise or consist of glass particles.
  • the powdered coating material comprises or consists of organic and/or inorganic salts.
  • the powdered coating material comprises or consists of plastic particles.
  • the above-named plastic particles are formed for example from pure or mixed homo-, co-, block or pre-polymers or mixtures thereof.
  • the plastic particles can 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 powdered coating material comprises or consists of mixtures of particles of different materials.
  • the powdered coating material consists in particular of at least two, preferably three, different particles of different materials.
  • the particles can be produced via different methods.
  • the metal particles can be obtained by spraying or atomizing molten metals.
  • Glass particles can be produced by mechanical comminution of glass or else from the melt. In the latter case, the glass melt can likewise be atomized or nebulized.
  • melted glass can also be comminuted on rotating elements, for example a drum.
  • Mineral particles, metal-oxide particles and inorganic particles which are selected from the group which consists of oxides, hydroxides, carbonates, carbides, nitrides, halides and mixtures thereof can be obtained by comminuting the naturally occurring minerals, stones, etc. and then screening them by size.
  • the screening by size can be carried out for example by means of cyclones, air separators, screens, etc.
  • the particles of the powdered coating material have been provided with a coating before they were covered with the additive.
  • the above-named coating can comprise a metal or consist of a metal.
  • a coating of a particle can be formed closed or particulate, wherein coatings with a closed structure are preferred.
  • the layer thickness of such a metallic coating preferably lies below 1 ⁇ m, more preferably below 0.8 ⁇ m and still more preferably below 0.5 ⁇ m.
  • such coatings have a thickness of at least 0.05 ⁇ m, more preferably of at least 0.1 ⁇ m.
  • Metals that are particularly preferred in particular embodiments for use in one of the above-named coatings are selected from the group consisting of copper, titanium, gold, silver, tin, zinc, iron, silicon, nickel and aluminum, preferably from the group consisting of gold, silver, tin and zinc, further preferably from the group consisting of silver, tin and zinc.
  • the term main constituent within the meaning of the above-named coating denotes that the relevant metal or a mixture of the above-named metals represents at least 90 wt.-%, preferably 95 wt.-%, further preferably 99 wt.-% of the metal content of the coating. It must be understood that, in the case of a partial oxidation, the oxygen proportion of the corresponding oxide layer is not taken into account.
  • Such metallic coatings can be produced for example by means of gas-phase synthesis or wet-chemical methods.
  • the particles according to the invention of the powdered coating material are additionally or alternatively coated with a metal oxide layer.
  • this metal oxide layer substantially consists of silicon oxide, aluminum oxide, boron oxide, zirconium oxide, cerium oxide, iron oxide, titanium oxide, chromium oxide, tin oxide, molybdenum oxide, oxide hydrates thereof, hydroxides thereof and mixtures thereof.
  • the metal oxide layer substantially consists of silicon oxide.
  • the above-mentioned term, “substantially consists of”, within the meaning of the present invention means that at least 90%, preferably at least 95%, more preferably at least 98%, still more preferably at least 99% and most preferably at least 99.9% of the metal oxide layer consists of the above-named metal oxides, in each case relative to the number of particles of the metal oxide layer, wherein any water contained is not factored in.
  • the composition of the metal oxide layer can be determined by means of methods known to a person skilled in the art, such as for example sputtering in combination with XPS or TOF-SIMS.
  • Such a metal oxide layer can be applied for example using the sol-gel method.
  • the substrate is selected from the group consisting of plastic substrates, inorganic substrates, cellulose-containing substrates and mixtures thereof.
  • the plastic substrates can be for example plastic films or shaped bodies made of plastics.
  • the shaped bodies can have geometrically simple or complex shapes.
  • the plastic shaped body can be for example a component from the automotive industry or the construction industry.
  • the cellulose-containing substrates can be cardboard, paper, wood, wood-containing substrates, etc.
  • the inorganic substrates can be for example metallic substrates, such as metal sheets or metallic shaped bodies or ceramic or mineral substrates or shaped bodies.
  • the inorganic substrates can also be solar cells or silicon wavers, to which for example electrically conductive coatings or contacts are applied.
  • Substrates made of glass such as for example glass panes, can also be used as inorganic substrates.
  • the glass, in particular glass panes, can be provided for example with electrochromic coatings using the method according to the invention.
  • the substrates coated by means of the method according to the invention are suitable for very different uses.
  • the coatings have optical and/or electromagnetic effects.
  • the coatings can bring about reflections or absorptions.
  • the coatings can be electrically conductive, semi-conductive or non-conductive.
  • Electrically conductive layers can be applied for example in the form of strip conductors to components. This can be used for example to make current-carrying possible within the framework of the on-board power supply in an automobile component. Furthermore, such a strip conductor can, however, also be formed for example as an antenna, as a shield, as an electrical contact, etc. This is particularly advantageous for example for RFID applications (radio frequency identification). Furthermore, coatings according to the invention can be used for example for heating purposes or for the targeted heating of specific components or specific parts of larger components.
  • the coatings produced act as sliding layers, diffusion barriers for gases and liquids, wear and/or corrosion protection layers.
  • 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 human-machine interface (HMI), for example in the form of a touchscreen.
  • HMI human-machine interface
  • the coatings can likewise be used to shield from electromagnetic interferences (EMI) or to protect against electrostatic discharges (ESD).
  • EMI electromagnetic interferences
  • ESD electrostatic discharges
  • the coatings can also be used to bring about electromagnetic compatibility (EMC).
  • layers can be applied which are applied for example to increase the stability of corresponding components after repair.
  • An example is repairs in the aviation sector, wherein for example a loss of material as a result of processing steps must be compensated for, or a coating is to be applied for example for stabilization.
  • This proves to be difficult for aluminum components for example, and normally requires post-processing steps such as sintering.
  • firmly adhering coatings can be applied under very gentle conditions, without post-processing steps such as sintering even being required.
  • the coatings act as electrical contacts and allow an electrical connection between different materials.
  • FIGS. 1 and 2 show a wafer, coated with solar contact paste, which has been coated with a powdered coating material according to the invention using 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 device (Sympatec, Germany). For the measurement, 3 g of the powdered coating material was introduced into the measuring device and treated, before the measurement, with ultrasound for 30 seconds. For the dispersion, a Rodos T4.1 dispersing unit was used, wherein the primary pressure was 4 bar. The evaluation was carried out with the device's standard software.
  • Example 2 The application of the additive was carried out analogously to Example 1. 2 g of an acrylic polymer based on methyl methacrylate and n-butyl methacrylate (Degalan LP AL 23, from Evonik) was used as additive.
  • the application of the coating excipient was carried out analogously to Example 4. 3 g monoethyl fumarate was used as coating excipient.
  • the application of the coating excipient was carried out analogously to Example 4. 3 g adipic acid monoethyl ester was used as coating excipient.
  • the application of the coating excipient was carried out analogously to Example 4. 3 g methyl triglycol was used as coating excipient.
  • the application of the coating excipient was carried out analogously to Example 4. However, copper particles with a D 50 of 34 ⁇ m were used here. 3 g adipic acid monoethyl ester was used as coating excipient.
  • the application of the coating excipient was carried out analogously to Example 4. However, a copper particle with a D 50 of 34 ⁇ m was used here. 3 g methyl triglycol was used as coating excipient.
  • Example 4 The application of the coating excipient was carried out analogously to Example 4. A copper particle with a D 50 value of 34 ⁇ m was used here. 3 g ethyl cellulose (Ethocel Standard 10, from Dow Wolff Cellulosics) was used as coating excipient.
  • Example 4 The application of the coating excipient was carried out analogously to Example 4. A copper particle with a D 50 value of 34 ⁇ m was used here. 3 g DEGALAN PM 381 (copolymer from methyl methacrylate and isobutyl methacrylate, from Evonik) was used as coating excipient.
  • the additive was applied analogously to Example 4. 100 g spherical tin particles with a D 50 of 28 ⁇ m were used here. 3 g Aerosil 200 (pyrogenic silicic acid, from Evonik) was used as additive.
  • an AS 100 fluidimeter from Sames was used. There, 250 g of the respective particles according to Examples 1 to 3 were poured in and fluidized with a gas. Nitrogen was used here as gas. A calibrated bore was then opened for 30 seconds and the weight (W) of the material that flowed out in this time was recorded as the measured variable.
  • the powdered coating material was applied by means of a Plasmatron system from Inocon, Attnang-Puchheim, Austria. Nitrogen was used as ionizable gas. Standard process parameters were used here. Wafers coated with a solar contact paste were used as substrate. Additive-covered tin particles according to Example 12 and analogous tin particles without additive served as powdered coating materials.
  • the metal sheets coated according to the invention were much more homogeneous in relation to their optics as well as their haptics. SEM photographs of the surfaces demonstrate the formation of larger uniform areas of the coating, while the surface of the comparison examples is characterized by a large number of isolated particles. Furthermore, the cross-section shows that cavities contained in the coating of the metal sheet according to the invention are significantly smaller.
US14/234,851 2011-07-25 2012-07-25 Methods for Substrate Coating and Use of Additive-Containing Powdered Coating Materials in Such Methods Abandoned US20140230692A1 (en)

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DE102011052119.4 2011-07-25
DE102011052120A DE102011052120A1 (de) 2011-07-25 2011-07-25 Verwendung speziell belegter, pulverförmiger Beschichtungsmaterialien und Beschichtungsverfahren unter Einsatz derartiger Beschichtungsmaterialien
DE102011052120.8 2011-07-25
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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JP2014527575A (ja) 2014-10-16
CN103827344A (zh) 2014-05-28
WO2013014213A2 (de) 2013-01-31
KR20140061422A (ko) 2014-05-21

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