EP2935641B1 - Verfahren zur beschichtung eines substrats mit einem abreibbaren keramischen material - Google Patents

Verfahren zur beschichtung eines substrats mit einem abreibbaren keramischen material Download PDF

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EP2935641B1
EP2935641B1 EP13811188.5A EP13811188A EP2935641B1 EP 2935641 B1 EP2935641 B1 EP 2935641B1 EP 13811188 A EP13811188 A EP 13811188A EP 2935641 B1 EP2935641 B1 EP 2935641B1
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Prior art keywords
ceramic compounds
solid particles
ceramic
coating
liquid phase
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English (en)
French (fr)
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EP2935641A1 (de
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Aurélie QUET
Luc Bianchi
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique CEA
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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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
    • 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
    • C23C4/123—Spraying molten metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/34—Applying different liquids or other fluent materials simultaneously
    • 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
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C23C4/11—Oxides
    • 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 invention relates to a method of coating at least one surface of a substrate with at least one ceramic compound.
  • the technical field of the invention can be defined, in particular, as that of the coating of substrates with an abradable material, and more particularly of the coating of substrates with a ceramic abradable material.
  • the coatings of an abradable ceramic material find their utility mainly in devices in which moving parts must be located as close as possible to fixed parts.
  • the deposition of a coating of an abradable ceramic material such as that produced according to the invention makes it possible, when the coating is brought into contact with a moving part, to use it in a preferential manner over the moving part.
  • the invention is likely to find its application, in general, in the field of mechanical engineering, and more particularly in the field of aeronautical design, such as, for example, for the protection of the integrity of the surface condition of fixed turbojet engine parts, such as low and high pressure compressors, turbines or stators.
  • the deposition, on a substrate, of a coating comprising at least one layer of an abradable material, or more simply the deposition of an “abradable coating”, is a technique frequently used in applications. fields such as mechanical engineering and aeronautical design.
  • abradable coating abradable material is generally meant that this coating or material wears preferentially with respect to the part located opposite, and is capable of being easily machined by moving parts.
  • Such coatings are, for example, used in automotive turbochargers, or else in the walls of land turbines and gas turbines of aeronautical engines.
  • the function of the abradable coating is the constitution of dynamic seals, which make it possible to minimize the play existing between the top of the rotating blades and the casing of the compressor or of the turbine ring.
  • the coating which is deposited on a stationary turbine element, the stator, wears out during contact with the top of the blades, whether the latter occurs during the running-in turns of the rotor or in the event of contact. accidental during service.
  • This coating then makes it possible to promote optimal operation of the turbojets, with reduced clearance and without damaging the structure of the blades.
  • thermal spraying A technique often used for the production of abradable coatings is thermal spraying.
  • thermal spraying processes are used in particular in research laboratories and in industry for the production, on very diverse substrates in terms of nature and shape, of deposits of ceramic, metallic and polymer materials, but also combinations of those. -this.
  • the compounds or precursors of compounds entering into the constitution of the coating are injected into a heat source which is produced by a projection gas, for example a mixture of a combustible gas and an oxidizing gas or a gas. ionized plasma type.
  • a projection gas for example a mixture of a combustible gas and an oxidizing gas or a gas. ionized plasma type.
  • the solid particles which are introduced or generated within the flame are partially or totally melted, then accelerated towards a substrate to form, on the surface of the latter, a coating by stacking solid particles and molten particles also called " Lamellae " (or " splats " in English terminology).
  • thermal spraying techniques to the production of abradable coatings makes it possible to generate two types of coating.
  • a first type of coating which is very porous, can be made by including unmelted particles in the coating.
  • this type of coating which turns out to be difficult to reproduce, does not have satisfactory properties for use as an abradable coating, namely correct mechanical strength and a porosity greater than or equal to. 20 percent (%).
  • the thermal spraying of solid particles which have an average particle size greater than 5 ⁇ m, for example by plasma spraying conventionally makes it possible to achieve porosities of between 5 and 20%.
  • a second type of coating, more dense, can be obtained, the porosity then being generated by the introduction of solid sacrificial particles, of organic or ceramic nature within the coating.
  • the document [4] of Clingman et al. describes a method for producing an abradable coating for turbine engine components, such as a compressor or a turbine shell.
  • the coating consists of a zirconium (IV) oxide matrix stabilized with an oxide chosen from among yttrium (III) oxide (Y 2 O 3 ), magnesium oxide (MgO) and oxide.
  • calcium (CaO) in which are dispersed particles of an easily decomposable crystalline aromatic polyester at a temperature above about 500 ° C.
  • the porosity of the coating obtained by this process is evaluated between 20 and 33%.
  • Rangaswamy et al. describes an abradable coating for gas turbine elements, comprising a matrix consisting of a metal or a mixture of metals chosen from aluminum, cobalt, copper, iron, nickel and silicon , a solid lubricant such as calcium fluoride (CaF 2 ), molybdenum disulfide (MoS 2 ) or boron nitride, and a pore-forming agent in the form of solid particles of graphite or of a polymer, such as an aromatic polyimide or a polyester selected from a p -oxy-benzoyl homopolyester and a poly ( p- oxybenzoylmethyl) ester.
  • a solid lubricant such as calcium fluoride (CaF 2 ), molybdenum disulfide (MoS 2 ) or boron nitride
  • MoS 2 molybdenum disulfide
  • boron nitride boronitride
  • the porosity within coatings of the second type can still be generated by combining the inclusion of ceramic particles and the creation of a network of cavities on the surface of the coating after thermal spraying.
  • the document [7] of Le Biez et al. discloses an abradable coating for gas turbine elements, comprising a matrix of a nickel-chromium-aluminum alloy in which hollow balls of an aluminum-silicate material are dispersed. A network of cavities is machined on the surface of the coating, which then has a porosity of at least 40%.
  • the document [9] of Lima et al. describes a process for preparing a coating for elements such as compressors or combustion chambers, which comprises thermal spraying of ceramic particles of YSZ in the form of agglomerates of nanometric size.
  • the projection parameters are controlled so that the particles, once deposited on the substrate to be coated, form porous agglomerates of micrometric size and made up of unmelted YSZ particles and included in a matrix of molten YSZ particles.
  • Allen's document [10] describes a process for producing an abradable coating for elements such as turbine shell sections. This process comprises the thermal spraying of an aqueous suspension comprising a precursor of a ceramic material, for example YSZ, and a lubricant in solid form, chosen from boron trichloride, urea, guanidine and others. organic nitrogen compounds.
  • a coating of an entirely ceramic abradable material makes it possible to achieve high operating temperatures, typically greater than 1000 ° C., which are frequently reached in fields such as aeronautics.
  • the inventors have therefore set themselves the goal of developing a process for preparing a coating which meets the criteria set out above in order to be able to be used as an abradable coating, namely in particular: an ability to be easily abraded while at the same time with a slow wear mechanism as well as resistance to erosion and at elevated temperatures while maintaining suitable mechanical properties.
  • a coating must have a porosity greater than or equal to 20%, while having a homogeneous thickness and structure.
  • the aim of the present invention is also to provide such a method which is simple, reliable, easy to implement, and in particular avoids the use of additives.
  • the aim of the present invention is also to provide a process for preparing an abradable coating which does not present the drawbacks, defects and disadvantages of the processes of the prior art and which resolves the problems of the processes of the prior art.
  • the method of the invention differs from the prior art because it combines the advantages provided on the one hand by the dry injection of solid particles of n ceramic compounds S 1 , ..., S n in a jet thermal and, on the other hand, by the simultaneous injection of a liquid phase conveying solid particles of p ceramic compounds L 1 , ..., L p and / or at least one precursor of the solid particles of p ceramic compounds L 1 , ..., L p .
  • the general and preferred operating conditions of the process of the invention are set out below.
  • the substrate can be organic, inorganic or mixed, that is to say that the same surface of the substrate, in particular the surface to be coated by the method according to the invention, can be both organic and inorganic.
  • the substrate withstands the operating conditions of the process of the invention.
  • the substrate consists of a TiAIV alloy (alloy of titanium, aluminum and vanadium), for example of TiAl 6 V (alloy composed of 90% by mass of Ti, 6% by mass of aluminum and 4% by mass of vanadium).
  • a TiAIV alloy alloy of titanium, aluminum and vanadium
  • TiAl 6 V alloy composed of 90% by mass of Ti, 6% by mass of aluminum and 4% by mass of vanadium
  • the surface of the substrate that is to be coated is optionally prepared and / or cleaned in order to remove organic and / or inorganic contaminants which would be liable to damage. 'to prevent the deposition or even fixation of the coating on the surface, and in order to improve the adhesion of the coating.
  • the method of preparing the surface may consist of creating a surface roughness by sandblasting.
  • the cleaning process used depends on the nature of the substrate and can be carried out by one or more technique (s) chosen from among the physical, chemical and mechanical techniques known to those skilled in the art.
  • the cleaning process can be carried out, for example, by a technique chosen from immersion in an organic solvent, laundry cleaning, acid pickling and the combination of two or more of these techniques, this or these techniques which can also be assisted by ultrasound.
  • the cleaning can optionally be followed by rinsing with tap water, then by rinsing with deionized water, the rinses optionally being followed by drying by a technique chosen from the “ lift-out ” technique. , an alcohol spray, a blast of compressed air, a blast of hot air, or infrared rays.
  • the expression “chemical element” designates an element of the periodic table of chemical elements, also known under the names of the periodic table of the elements or the Mendele ⁇ ev table, while the expression “compound chemical ”denotes an ionic molecule or compound formed from at least two different chemical elements.
  • ceramic compound In the context of the present invention, the definition of the expression “ceramic compound” is not repeated and is well known to a person skilled in the art.
  • metal and metalic refer to the elements which are classically considered as metals in the periodic table of the elements, in particular the transition elements (such as, for example, titanium, zirconium, niobium, yttrium, vanadium, chromium, cobalt and molybdenum), other metals (such as aluminum, gallium, germanium and tin), lanthanides and actinides. These terms also refer to metalloid elements such as, for example, silicon.
  • the process comprises, in step a), the simultaneous injection of solid particles of n ceramic compounds S 1 , ..., S n suitably chosen, and of a liquid phase comprising a solvent, solid particles of p ceramic compounds L 1 , ..., L p and / or at least one precursor of the solid particles of p ceramic compounds L 1 , ..., L p suitably chosen.
  • each of the n ceramic compounds S 1 , ..., S n and of the p ceramic compounds L 1 , ..., L p comprises at least one element chosen in the periodic table of elements from the elements of transition, metalloids and lanthanides.
  • each of the n ceramic compounds S 1 , ..., S n and of the p ceramic compounds L 1 , ..., L p is chosen from oxides, silicates and zirconates of at least one element chosen in the periodic table of elements from among the transition elements, metalloids and lanthanides.
  • each of the n ceramic compounds S 1 , ..., S n and of the p ceramic compounds L 1 , ..., L p is chosen from simple oxides, silicates and zirconates of at least one selected element among aluminum, silicon, titanium, strontium, zirconium, barium, hafnium and elements of the “rare earth” family as defined by the International Union of Pure and Applied Chemistry (cf. [11] ), ie scandium, yttrium and lanthanides.
  • solid particle is used to designate a particle in solid form, at ambient pressure and temperature, the ambient temperature being defined as being the temperature at which the particle is located when that it is not subjected either to cooling or to any heating.
  • the ambient temperature is generally 15 to 30 ° C, for example 20 to 25 ° C.
  • the solid particles of the n ceramic compounds S 1 , ..., S n are particles which can be of any shape, but of which at least 90% by number have a greater dimension greater than 5 ⁇ m and less than 100 ⁇ m.
  • the largest dimension of a particle corresponds to the diameter of the latter when it is established, for example by a reproducible particle size analysis, that the particle has or has substantially the shape of a sphere.
  • the liquid phase results from bringing a solvent into contact with solid particles of the p ceramic compounds L 1 , ..., L p and / or at least one precursor of the solid particles of the p ceramic compounds L 1 , ..., L p .
  • precursor is generally meant at least one chemical compound used in any one of the chemical reactions by which the p ceramic compounds L 1 , ..., L p (which are in the form of solid particles) are obtained.
  • the liquid phase can advantageously result from placing in solution or, as a variant, suspending, in a solvent, solid particles of p ceramic compounds L 1 , ..., L p and / or d 'at least one solid particle precursor of the p ceramic compounds L 1 , ..., L p , it being specified that at least 90% by number of the solid particles of each of the p compounds L 1 , ..., L p has a greater dimension less than or equal to 5 ⁇ m .
  • the liquid phase obtained can be a true solution or, as a variant, a colloidal solution of the solid particles of the p ceramic compounds L 1 , ..., L p and / or at least a precursor of the solid particles of the p ceramic compounds L 1 , ..., L p .
  • a chemical compound and in particular, a ceramic compound or a ceramic compound precursor, is soluble in a solvent when it is able to form a true solution or a colloidal solution with this solvent.
  • a true solution when the solute is a small molecule
  • we speak more of a colloidal solution when the solute is a macromolecule size ranging from 5 nanometers (nm) to 1 ⁇ m, cf. [12] ).
  • the solvent is chosen from water, organic solvents (for example, ethanol), mixtures of water and at least one organic solvent miscible with water (for example, a water-ethanol mixture ) and mixtures of organic solvents miscible with one another.
  • organic solvents for example, ethanol
  • mixtures of water and at least one organic solvent miscible with water for example, a water-ethanol mixture
  • the liquid phase is a colloidal aqueous solution of the solid particles of the p ceramic compounds L 1 , ..., L p and / or at least one precursor of the solid particles of the p ceramic compounds L 1 , ..., L p .
  • integers n and p which are identical or different, are chosen one independently of the other. These integers n and p are chosen from an interval ranging from 1 to 10, better still, from an interval ranging from 1 to 5, all the intermediate values included in the intervals thus defined being considered.
  • the n ceramic compounds S 1 , ..., S n can all be identical to the p ceramic compounds L 1 , ..., L p , and the integer n is then equal to the integer p.
  • the n ceramic compounds S 1 , ..., S n injected by the first injection means are exactly the same as the p ceramic compounds L 1 , ..., L p which are injected by the second injection means, or which are obtained in the thermal jet after the chemical reaction (s) of formation of the p ceramic compounds L 1 , ..., L p (in the case where they are precursors of these p ceramic compounds L 1 , ..., L p which are injected by the second injection means).
  • n and p are both equal to 1
  • the ceramic compounds S 1 and L 1 are both mullite.
  • It is a crystalline aluminosilicate existing in the form of a solid solution of composition Al 2 [Al 2 + 2 x Si 2-2 x ] O 10- x with 0.17 ⁇ x ⁇ 0.5.
  • the composition of this aluminosilicate can thus change between the “3: 2 mullite” (3 Al 2 O 3 ⁇ 2 SiO 2 ) and “2: 1 mullite” (2 Al 2 O 3 ⁇ SiO 2 ) forms, the different stoichiometries being obtained by substitution of silicon atoms by aluminum atoms within the crystal.
  • the liquid phase is an aqueous colloidal mullite solution, which can be prepared, for example, by suspending solid particles of aluminum nitrate, an aqueous suspension of colloidal particles of silica and water. deionized.
  • the n ceramic compounds S 1 , ..., S n may be partially or totally different from the p ceramic compounds L 1 , ..., L p , the integer n then not necessarily being equal to the whole p.
  • the combination of ceramic compounds exhibiting various intrinsic properties can be carried out for the purpose of optimizing the in situ behavior of the coating obtained by the process of the invention (for example, by conferring properties of mechanical resistance at temperatures high ie typically greater than 1000 ° C).
  • step a) the injection of step a) is carried out in a thermal jet, whereby a mixture of the solid particles of the n ceramic compounds S 1 , ..., S n and of the liquid phase is obtained in the thermal jet.
  • the nature of the projection gas is chosen as a function of the thermal jet projection technique which is used.
  • the projection gas can be a mono- or polyatomic gas or else a mixture of gases, as defined below.
  • the simultaneous injection of the solid particles of the n ceramic compounds S 1 , ..., S n and of the liquid phase can be carried out by any suitable means of injection of solids and liquids.
  • a first injection means can be connected to a reservoir (s) containing the solid particles of the n ceramic compounds S 1 , ..., S n
  • a second injection means can be connected to a reservoir (s) containing the liquid phase.
  • the solid particles of the n ceramic compounds S 1 , ..., S n can be injected into the thermal jet in the form of a jet of these particles, and the liquid phase can be injected in the form of 'a jet or drops, preferably with a quantity of movement adapted to be substantially identical to that of the thermal jet.
  • the rate of porosity can be adjusted by varying the distance D S -D L.
  • the mobilization of the energy of the thermal jet is greater for the vaporization of the liquid phase than for the fusion of the solid particles of the n ceramic compounds S 1 , ..., S n .
  • the liquid phase is injected into the thermal jet at a distance from the substrate which is less than or equal to the distance from the substrate at which the solid particles of the n ceramic compounds S 1 , ..., S n are injected into the substrate. the thermal jet.
  • the injection distances into the thermal jet are preferably chosen so as to satisfy the following inequality: D S ⁇ D L.
  • the vaporization of a solvent in fact mobilizes a large amount of the energy of the jet and promotes faster extinction of the plasma jet, i.e., the length of the plasma jet decreases (variable depending on the nature of the jet. solvent, ethanol mobilizing less energy than water for example).
  • the injection of the liquid phase is done upstream, there is not enough energy available to melt the solid particles downstream.
  • Sufficient energy remains available downstream for the vaporization of the solvent and the treatment of the liquid phase.
  • the temperature of the solid particles of the n ceramic compounds S 1 , ..., S n during their injection into the thermal jet can be the ambient temperature as already defined above, for example 20 ° C.
  • the temperature of these particles can be controlled and modified for their injection into the thermal jet, for example so that it is within a range of 20 to 150 ° C.
  • the solid particles can in particular be preheated before injection in order to overcome any problems of relative humidity which can cause the solid particles to agglomerate and reduce the flowability of the powder.
  • the temperature of the liquid phase during its injection into the thermal jet can range, for example, from ambient temperature, for example 20 ° C., to a temperature below the boiling point of this liquid phase.
  • it is possible to control and modify the temperature of the liquid phase for its injection into the thermal jet for example to be from 1 to 99 ° C.
  • the liquid phase then has a different surface tension, which results in a more or less rapid and effective fragmentation mechanism when it arrives in the thermal jet. The temperature can therefore have an effect on the quality of the coating obtained.
  • the method also comprises a step b), in which a projection of the thermal jet, which contains the mixture of the solid particles of the n ceramic compounds S 1 , ..., S n and the liquid phase, is carried out. on the substrate, whereby, a layer comprising at least one ceramic compound is formed on the substrate.
  • the projection of the thermal jet groups together all the processes by which the solid constituents of a material (or “filler material”), here the solid particles of the n compounds ceramics S 1 , ..., S n and those possibly in suspension in the liquid phase, are melted or brought to the plastic state by means of a heat source or enthalpy source.
  • the mixture formed in the thermal jet is then projected onto the substrate to be coated onto which it adheres mechanically and solidifies (without causing the substrate melting phenomenon).
  • the latter can be deposited on the substrate in the form of a layer by the implementation of thermal spraying processes as stated below. -after.
  • the deposition can be carried out by a flame projection process using a projection gas.
  • the flame projection process is chosen from a flame-powder projection process and a hypersonic flame projection process, with continuous or discontinuous firing (HVOF or “ High Velocity Oxy Fuel ” process, HVAF or “ High Velocity Air Fuel ” process. ).
  • the projection gas is brought to a temperature of between 3,000 and 3,500 Kelvin (K).
  • the deposition can be carried out by a plasma arc blown projection process using a plasma gas.
  • the thermal jet which is then a plasma jet, can be generated by a plasma gas which is advantageously chosen from argon, helium, dinitrogen, dihydrogen, binary mixtures thereof, such as an argon-helium mixture or an argon-dihydrogen mixture, and ternary mixtures of these, such as an argon-helium-dihydrogen mixture, the latter mixture being very particularly preferred.
  • a plasma gas which is advantageously chosen from argon, helium, dinitrogen, dihydrogen, binary mixtures thereof, such as an argon-helium mixture or an argon-dihydrogen mixture, and ternary mixtures of these, such as an argon-helium-dihydrogen mixture, the latter mixture being very particularly preferred.
  • the plasma generation method is chosen from an arc plasma, blown or not, an inductive or radiofrequency plasma, for example in supersonic mode.
  • the generated plasma can operate at atmospheric pressure or at lower pressure.
  • the device which is used to generate the plasma is an arc plasma torch.
  • the projection gas is brought to a temperature of between 5,000 and 15,000 K.
  • the projection gas has a viscosity ranging from 10 -4 to 5.10 -4 kilograms per meter second (kg / m ⁇ s).
  • the deposition is carried out by a blown arc plasma projection process.
  • the solid particles of the n ceramic compounds S 1 , ..., S n and the liquid phase simultaneously enter the thermal jet.
  • the kinetic and thermal energies of the thermal jet serve on the one hand to partially or totally melt the solid particles of the n ceramic compounds S 1 , ..., S n , and on the other hand, to split the liquid phase into a plurality of droplets under the effect of the shear forces of the thermal jet, vaporize the solvent from the liquid phase and lead to obtaining solid particles of the p ceramic compounds L 1 , ..., L p which are partially or totally melted .
  • the mixture formed by the partially solid particles or completely molten ceramic compounds S 1 , ..., S n , L 1 , ..., L p and the droplets of solvent of the liquid phase is accelerated to be collected on the substrate, in the form of a deposit which constitutes the coating.
  • the temperature of the thermal jet is chosen as a function of the chemical nature of the species which make up the mixture and of the desired coating.
  • the temperature can be chosen so as to be in a melting configuration partial solid particles of the mixture, in order to best conserve the starting properties within the layer (s) which make up the coating.
  • the total fusion of the particles makes it possible to obtain a non-transformable and therefore stable phase, generally very interesting for the targeted applications.
  • the substrate to be coated is, for obvious reasons, preferably positioned relative to the thermal jet so that the projection of the mixture is directed onto the surface to be coated. Positioning is adjusted for each application, depending on the selected spray conditions and the desired deposit microstructure.
  • the or each of the layers comprising at least one ceramic compound which can be deposited by the method of the invention may have a thickness ranging from 10 ⁇ m to 2 mm.
  • the inventors have also observed that the porosity of the deposited layer (s) was closely linked to parameters relating to the liquid phase, such as the volume proportion of solid particles of the p ceramic compounds L 1 , ... , L p and / or precursors of these ceramic compounds in the liquid phase, or the rate with which the liquid phase is injected into the thermal jet.
  • the volume proportion of solid particles of p ceramic compounds L 1 , ..., L p and / or of precursors of these ceramic compounds in the liquid phase is between 2% and 20%.
  • the ratio of the volume of the solid particles of the n ceramic compounds S 1 , ..., S n to the volume of the solid particles of the p ceramic compounds L 1 , ..., L p is within a range of 0.4 to 3.
  • the flow rate with which the liquid phase is injected into the thermal jet is (0.05 ⁇ 0.03) liters per minute (L / min).
  • the or each of the layers comprising at least one ceramic compound has a plurality of pores having a size of between 0.001 and 50 micrometers.
  • the physicochemical characteristics of the plurality of pores are described later.
  • the inventors have further observed that by subjecting a coating as obtained by the process of the invention to temperatures above 1000 ° C. - typically operating temperatures of the devices in which these coatings are integrated - the porosity of the coating was not reduced.
  • the inventors have in fact observed that consolidation of the coating was observed at such temperatures.
  • the consolidation which is caused by the phenomena of sintering and coalescence of the solid particles included in the deposit and of the pores formed within the deposit, is a reorganization of the areas of material and of the porous areas, without reducing the total volume. porous.
  • the process of the invention thus makes it possible to obtain a coating resistant to erosion, while retaining very appreciable mechanical properties at high temperatures. It also makes it possible to obtain a coating of controlled porosity greater than or equal to 20%, which allows the latter to be used as an abradable coating.
  • the overall porosity of the coating ie the porosity of the layer (s) comprising at least one ceramic compound, which is / are deposited by carrying out the method of the invention
  • the overall porosity of the coating must not be too greater than 20%, because a coating having too high a porosity is subject to too rapid wear of the deposits of ceramic abradable material and hardly constitutes a durable solution for use as an abradable coating in the aforementioned fields.
  • the or each of the layers comprising at least one ceramic compound has a porosity at least equal to 20%; preferably at least equal to 20%, and at most equal to 40%, for example 35%.
  • each of the layers must have a porosity at least equal to 20%; and preferably between 20% and 40%, for example 35%, so that the assembly can be used as an abradable coating.
  • the method of the invention also makes it possible to obtain a structured coating while advantageously controlling other properties, such as a thickness of the homogeneous deposit on a substrate of complex shape, or the possibility of depositing on any type of substrate. , whatever their nature and roughness.
  • an R 1 coating is produced on a substrate made of TiAIV (alloy of titanium, aluminum and vanadium) by blown arc plasma projection of solid mullite particles, but without injection of a liquid phase, all the other parameters. otherwise remaining identical to those used for the production of R m .
  • an R 2 coating is produced on a substrate made of TiAIV (alloy of titanium, aluminum, and vanadium) by plasma arc projection blown from a colloidal aqueous solution containing precursors of solid mullite particles, but without injection of solid mullite particles.
  • TiAIV alloy of titanium, aluminum, and vanadium
  • an R 3 coating is produced on a substrate consisting of TiAIV (alloy of titanium, aluminum, and vanadium) by blown arc plasma projection of a mixture produced by simultaneous injection, into the plasma jet, of a on the one hand solid mullite particles and on the other hand deionized water containing neither solid mullite particles nor precursors of solid mullite particles, the injection of water into the plasma jet being carried out at a distance D L from the substrate such that the following inequality is satisfied: D S ⁇ D L.
  • an R 4 coating is produced by depositing, on the surface of a substrate made of TiAIV (alloy of titanium, aluminum, and vanadium), a first layer having the composition of R 1 , then of a second layer having the composition of the coating R m in accordance with the invention.
  • TiAIV alloy of titanium, aluminum, and vanadium
  • the spraying process of the present invention can be easily industrialized since its specificity and its innovative character reside in particular in the injection system, which can be adapted to all thermal spraying machines already present in industry; in the nature of the species which are injected simultaneously into the thermal jet; but also in the choice of the operating conditions imposed on the thermal jet, to obtain a structured coating which has the properties of the ceramic compound (s) constituting it.
  • each of the n ceramic compounds S 1 , ..., S n and of the p ceramic compounds L 1 , ..., L p comprises at least one element chosen in the periodic classification of the elements from among transition elements, metalloids and lanthanides.
  • each of the n ceramic compounds S 1 , ..., S n and of the p ceramic compounds L 1 , ..., L p is chosen from simple oxides, silicates and zirconates of at least an element selected in the periodic table of elements from among the transition elements, metalloids and lanthanides.
  • each of the n ceramic compounds S 1 , ..., S n and of the p ceramic compounds L 1 , ..., L p is chosen from simple oxides, silicates and zirconates of at least one selected element among aluminum, silicon, titanium, strontium, zirconium, barium, hafnium and elements of the "rare earth" family as defined by the International Union of Pure and Applied Chemistry, it ie scandium, yttrium and lanthanides.
  • each of the n ceramic compounds S 1 , ..., S n and of the p ceramic compounds L 1 , ..., L p is chosen from the ceramic compounds which are usually used in the composition of thermal barriers and which have been previously cited in the description of the process of the invention.
  • the or each of the layers comprising at least one ceramic compound which is / are included in the coating according to the invention has a thickness ranging from 10 ⁇ m to 2 mm.
  • said or each of said layer (s) of the coating as defined above always has a porosity at least equal to 20%, preferably at least equal to 20% and at most equal to 40%, for example 35%, after submission of that (s) -ci at a temperature above 1000 ° C.
  • the torch is a plasma torch and the thermal jet is a plasma jet.
  • plasma gases are given above, reservoirs for these gases are commercially available. The reasons for these advantageous choices have been explained above.
  • the plasma torch is capable of producing a plasma jet having a temperature ranging from 5,000 to 15,000 K.
  • the plasma torch is capable of producing a plasma jet having a viscosity ranging from 10 -4 to 5.10 -4 kg / m s.
  • the device of the invention comprises two reservoirs, the first containing the solid particles of the n ceramic compounds S 1 , ..., S n , the second containing the liquid phase being pressurized and comprising solid particles of the p ceramic compounds L 1 , ..., L p and / or at least one precursor of the solid particles of the p ceramic compounds L 1 , ..., L p .
  • the device of the invention further comprises a cleaning tank containing a solution for cleaning the piping and the injection means.
  • a cleaning tank containing a solution for cleaning the piping and the injection means.
  • the injection system comprises pipes making it possible to convey the solid particles of the n ceramic compounds S 1 , ..., S n from the first reservoir to the first injection means. The same is true for the routing of the liquid phase from the second reservoir to the second injection means.
  • the first reservoir which contains the solid particles of the n ceramic compounds S 1 , ..., S n is connected to a carrier gas, which is for example argon, under the effect of which these particles are conveyed to the first means injection.
  • a carrier gas which is for example argon
  • the reservoir which contains the liquid phase is connected to a compressed air network by means of pipes and to a source of compression gas, for example compressed air.
  • a pressure regulator makes it possible to adjust the pressure inside the liquid phase tank, generally to a pressure less than or equal to 600 kilopascals (kPa).
  • a pump is also usable.
  • the liquid phase is conveyed to the second injection means by pipes and then leaves the second injection means, for example in the form of a jet of liquid which breaks up mechanically under the droplet form.
  • the flow rate and the amount of movement of the liquid phase at the outlet of the second injection means depend in particular on the pressure in the reservoir used and / or on the pump, on the characteristics of the dimensions of the nozzle of the injection means, and on the rheological properties of the liquid phase (for example, the mass proportion of solid particles of p ceramic compounds L 1 , ..., L p and / or precursors of these ceramic compounds).
  • the two injection means make it possible to inject the solid particles of the n ceramic compounds S 1 , ..., S n and the liquid phase into the thermal jet.
  • the device can be provided with a number of injection means greater than two, for example according to the quantities or the composition of the solid particles of the n ceramic compounds S 1 , ..., S n and phase liquid to be injected.
  • the injection of the solid particles of the first ceramic compound and of the liquid phase is carried out at an angle ⁇ with respect to the longitudinal axis of the thermal jet.
  • the angles ⁇ S and ⁇ L defined above in relation to the method are between 70 ° and 105 °, for example 90 °.
  • the injection line for the solid particles of the first ceramic compound and of the liquid phase can be thermostatically controlled so as to control, and optionally modify, the injection temperature of the latter. This temperature control and this modification can be carried out at the level of the pipes and / or at the level of the tanks (or compartments).
  • the device may include a means for fixing and moving the substrate relative to the torch.
  • This means can consist of clamps, screws, adhesives or equivalent system making it possible to fix the substrate and to maintain it during thermal spraying in a chosen position, and in a means making it possible to move in rotation and in translation the surface of the substrate facing the thermal jet and in the longitudinal direction of the plasma jet.
  • the device makes it possible to carry out direct and simultaneous injection thanks to a well-suited injection system, for example by using the device of the invention, of solid particles of the first ceramic compound and of a liquid phase containing at least one. second ceramic compound, the nature of the elements injected and the simultaneity of the injections contributing to the constitution of a ceramic coating having a porosity greater than 20%.
  • the scale worn on the Figure 13 represents 100 ⁇ m.
  • the porosity of the coating R m is then compared with that of the coatings R 1 , R 2 and R 3 prepared according to the processes according to the prior art.
  • the stability of the coating R m is evaluated after being subjected to a heat treatment at a temperature of 1300 ° C.
  • solid mullite particles and a liquid phase in the form of a colloidal aqueous solution comprising precursor compounds of solid mullite particles are injected simultaneously into a plasma of arc blown from a ternary argon-helium-dihydrogen mixture, the composition of which is specified below.
  • the injection system 13 involves a first reactor 14 composed of solid mullite particles 15 which come from the tank 17.
  • the assembly formed of the reactor 14 and the tank 17 is of the type of that of the particle distributors. solids which are marketed by the company Sulzer-Metco.
  • the particle size analysis of the solid particles of mullite 15 is carried out by laser particle size distribution using a Mastersizer 2000 device (Malvern company), and is shown on Figure 2 .
  • the cumulative rejections relating to a larger particle size of 49.0; 27.6 and 10.5 ⁇ m are respectively 10; 50 and 90%.
  • 10%; 50% and 90% by number of the solid mullite particles respectively have a greater dimension greater than 49.0; 27.6 and 10.5 ⁇ m.
  • the solid particles of mullite 15 are driven from the reactor 14 under the effect of a flow of carrier gas, in this case argon, with a flow rate of 4 ⁇ 10 -3 cubic meters per minute ( m 3 / min), the supply of which is provided via an inlet pipe 19.
  • the solid mullite particles 15 are then conducted, via an outlet pipe 20, from the reactor 14 to a first means of injection 21 which has an injection nozzle 22 at its end.
  • the injection system 13 involves a second reactor 23, intended for mixing a liquid phase which comprises compounds which are precursors of solid mullite particles.
  • the liquid phase is, in this case, a colloidal aqueous solution 24 comprising compounds which are precursors of solid mullite particles.
  • An aqueous colloidal sol of mullite is prepared.
  • the colloidal aqueous solution 24 which is placed in the reactor 23 has a mass proportion of compounds which are precursors of solid mullite particles of 15%. It is then homogenized using a magnetic stirring device 25.
  • the second reactor 23 is also equipped with a pressure regulator 26 which makes it possible to adjust the pressure inside the latter, and which is connected to a compression gas, here compressed air, the input of which is provided by means of a hose 27.
  • a pressure regulator 26 which makes it possible to adjust the pressure inside the latter, and which is connected to a compression gas, here compressed air, the input of which is provided by means of a hose 27.
  • the second reactor 23 is also equipped with a valve 28, as well as a pipe 29 connecting the interior of the reactor 23 to a tank 30 containing a cleaning liquid 31, here deionized water.
  • the valve 28 is closed and the colloidal aqueous solution 24 is expelled from the reactor 23 under the effect of a pressure of 300 kPa which is imposed by the pressure regulator 26 and the compression gas circulating via the pipe 27.
  • the colloidal aqueous solution 24 is then conducted, via an outlet pipe 32, from the reactor 23 to a second injection means 33 which has an injection nozzle 34 at its end.
  • the simultaneous injection of the solid particles of mullite 15, and of the colloidal aqueous solution 24 is carried out in a plasma jet 35, generated by an arc plasma blown at an intensity of 650 amperes (A) and coming from the plasma torch 10 by the projection nozzle 36, the latter being located at a distance D of 100 millimeters (mm) relative to the substrate 11.
  • the plasma gas, from which the plasma jet 35 is generated, is a ternary mixture composed in volume proportions of 50.8% argon, 23% helium and 8% dihydrogen.
  • the injection of the solid mullite particles 15 into the thermal jet 35 is carried out via the outlet orifice of the injection nozzle 22 of the first injection means 21, with a diameter of 1.5 mm, which implies, in light of the preceding data, a flow rate of solid mullite particles of 15 grams per minute (g / min).
  • This injection is carried out with an angle ⁇ S formed by the directions of the axis of inclination of the first injection means 21 and of the longitudinal axis of the plasma jet 35, equal to 90 °, and at a distance D S of 94 mm with respect to the substrate 11.
  • the injection of the colloidal aqueous solution 24 into the thermal jet 35 is carried out via the outlet orifice of the injection nozzle 34 of the second injection means 33, with a diameter of 250 ⁇ m.
  • This injection is carried out with an angle ⁇ L formed by the directions of the axis of inclination of the second injection means 33 and of the longitudinal axis of the plasma jet 35, equal to 90 °, and at a distance D L of 80 mm from the substrate 11.
  • the thickness of the deposits obtained is between 50 and 1000 ⁇ m.
  • the Figure 3 is a schematic representation of the structure of the coating R m , which includes solid mullite particles 37 defining a network of macropores 38 of size between 1 and 50 ⁇ m and said macropores being at least partially occupied by solid mullite particles which are generated within the plasma jet 35 from the mullite precursors contained in the colloidal aqueous solution 24, and which define a network 39 of micropores of size between 0.001 and 1 ⁇ m.
  • the cliché of the Figure 6 performed by SEM makes it possible to observe a structured deposit with two networks of pores (macro- and micropores) such as just described to comment on the Figure 3 .
  • the network 39 of micropores exhibits poor mechanical integrity, disrupts the arrangement of particles 37 and contributes significantly to the overall porosity of the coating R m .
  • Three coatings R 1 , R 2 and R 3 based on mullite are prepared by implementing methods of the prior art, in order to compare the properties of these coatings with those of the coating R m in accordance with the invention, in particular by terms of porosity.
  • the plasma projection parameters which are used to produce R 1 , R 2 and R 3 are identical to those used to produce R m .
  • the only modified parameter is the nature of the compounds which are injected into the plasma jet 35, before impact on the substrate 11 on which the coating is applied.
  • R 1 is produced by blown arc plasma projection of solid mullite particles 15, but without injection of a liquid phase into the plasma jet 35.
  • R 2 is produced by blown arc plasma spraying of an aqueous colloidal solution 24 which contains precursors of solid mullite particles, but without injection of solid mullite particles 15 into the plasma jet.
  • R 3 is produced by blown arc plasma spraying of a mixture obtained within the plasma jet 35, by simultaneous injection of solid particles of mullite 15, and deionized water containing neither solid particles of mullite nor particle precursors mullite solids.
  • the injection of the deionized water into the plasma jet 35 is carried out at a distance D L from the substrate such that the following inequality is satisfied: D S ⁇ D L.
  • the overall porosity of the R 1 , R 2 , R 3 and R m coatings is determined by the hydrostatic thrust method, in accordance with standard NF EN 623-2 (entitled “Advanced technical ceramics - Monolithic ceramics - General and textural properties”, in particular method n ° 1 under vacuum of part 2 entitled: “Determination of density and porosity”).
  • the overall porosity of 7% measured for R 1 is low and characteristic of a coating obtained by plasma spraying of solid particles on a substrate, without injection of a liquid phase.
  • the overall porosity measured for R 3 is 15%, i.e. almost double that of R 1 .
  • the deionized water which is injected into the plasma jet 35 appears to constitute a disturbing element of the lamellae of solid mullite particles 15 which are deposited on the substrate 11.
  • the disturbance then constitutes a factor in increasing the overall porosity of the coating.
  • the R 2 coating which is obtained is finely structured in the form of a very porous network.
  • the overall porosity of the coating R m in accordance with the invention is 35%, and is thus even greater than those of R 1 and R 3 .
  • the R m coating applied to a substrate made of TiAIV is subjected to a heat treatment for 24 hours at a temperature of 1300 ° C.
  • the Figure 12 is a schematic representation of the microstructure of the coating R m after heat treatment, which includes a first network of pores 44, formed within the stack of solid mullite particles in molten form 43. Around the pores 44, articulates a network 45 of pores, of smaller size, which results from the reorganization, at the end of the heat treatment, of the network 39 of pores ( Figure 3 ).
  • the cliché of the Figure 15 (carried out by SEM) makes it possible to observe a structured deposit with two networks of pores (macro- and micropores), which includes solid particles of mullite in molten form 43 defining a network of macropores 44 and said macropores being at least partly occupied by solid mullite particles which are generated within the plasma jet 35 from the mullite precursors contained in the colloidal aqueous solution 24, and which define a network 45 of micropores.
  • the network 45 of micropores has poor mechanical integrity, disrupts the arrangement of the network of macropores 44 and contributes significantly to the overall porosity of the coating R m .

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Claims (9)

  1. Verfahren zum Beschichten von zumindest einer Oberfläche eines Substrats mit zumindest einer Schicht, die zumindest eine keramische Verbindung enthält, wobei das Verfahren dadurch gekennzeichnet ist, dass es die folgenden Schritte umfasst:
    a) gleichzeitiges Einspritzen
    - von Feststoffteilchen (15) aus n keramischen Verbindungen S1, ..., S n durch ein erstes Einspritzmittel (21), wobei n eine ganze Zahl größer oder gleich 1 ist und zumindest 90 Zahlenprozent (%) der Feststoffteilchen (15) der n keramischen Verbindungen S1, ..., S n eine größte Abmessung von über 5 Mikrometer (µm) und unter 100 µm aufweisen; und
    - von einer flüssigen Phase (24) durch ein zweites Einspritzmittel (33), wobei die flüssige Phase ein Lösungsmittel, Feststoffteilchen aus p keramischen Verbindungen L1, ..., L p und/oder zumindest einen Vorläufer der Feststoffteilchen der p keramischen Verbindungen L1, ..., L p enthält, wobei p eine ganze Zahl größer oder gleich 1 ist und zumindest 90 Zahlenprozent der Feststoffteilchen der p keramischen Verbindungen L1, ..., L p eine größte Abmessung kleiner oder gleich 5 µm aufweisen,
    in einen thermischen Strahl (35), wodurch im thermischen Strahl (35) ein Gemisch aus den Feststoffteilchen (15) der n keramischen Verbindungen S1, ..., S n und der flüssigen Phase (24) erhalten wird; dann
    b) Aufspritzen des thermischen Strahls (35), der das Gemisch aus den Feststoffteilchen (15) der n keramischen Verbindungen S1, ..., S n und der flüssigen Phase (24) enthält, auf die genannte Oberfläche des Substrats (11), wodurch die Schicht, die zumindest eine keramische Verbindung enthält, auf der genannten Oberfläche gebildet wird;
    wobei gegebenenfalls die Aufeinanderfolge der Schritte a) und b) ein oder mehrere Male wiederholt wird;
    wobei die granulometrische Analyse der Feststoffteilchen mittels Lasergranulometrie erfolgt.
  2. Verfahren nach Anspruch 1, wobei
    jede der n keramischen Verbindungen S1, ..., S n und der p keramischen Verbindungen L1, ..., L p zumindest ein Element, ausgewählt aus dem Periodensystem der Elemente aus Übergangselementen, Metalloiden und Lanthaniden, enthält; wobei vorzugsweise jede der n keramischen Verbindungen S1, ..., S n und der p keramischen Verbindungen L1, ..., L p ausgewählt ist aus Oxiden, Silikaten und Zirkonaten zumindest eines Elements, ausgewählt aus dem Periodensystem der Elemente aus Übergangselementen, Metalloiden und Lanthanoiden; wobei weiterer vorzugsweise jede der n keramischen Verbindungen S1, ..., S n und der p keramischen Verbindungen L1, ..., L p ausgewählt ist aus einfachen Oxiden, Silikaten und Zirkonaten zumindest eines Elements, ausgewählt aus Aluminium, Silizium, Titan, Strontium, Zirkonium, Barium, Hafnium, Scandium, Yttrium und Lanthanoiden; wobei besser jede der n keramischen Verbindungen S1, ..., S n und der p keramischen Verbindungen L1, ..., L p ausgewählt ist aus den folgenden keramischen Verbindungen:
    - einem einfachen Oxid eines Elements, ausgewählt aus Zirkonium, Hafnium, Scandium, Yttrium und Lanthaniden, wobei die einfachen Oxide von Zirkonium und Hafnium mit einem Yttriumoxid stabilisiert sein können;
    - einem Silikat zumindest eines Elements, ausgewählt aus Aluminium, Yttrium, Scandium und Lanthaniden, wobei das Silikat mit zumindest einem Oxid von zumindest einem Element aus der zweiten Spalte des Periodensystems der Elemente dotiert sein kann;
    - einem Zirkonat zumindest eines Elements, ausgewählt aus Yttrium, Scandium und Lanthaniden, wobei das Zirkonat aus solchen ausgewählt ist, die gemäß einer Pyrochlor- oder Perowskitstruktur kristallisieren;
    und den Gemischen dieser keramischen Verbindungen.
  3. Verfahren nach einem der vorangehenden Ansprüche, wobei die flüssige Phase (24) eine kolloidale wässrige Lösung der Feststoffteilchen der p keramischen Verbindungen L1, ..., L p und/oder zumindest eines Vorläufers der Feststoffteilchen der p keramischen Verbindungen L1, ..., L p ist.
  4. Verfahren nach einem der vorangehenden Ansprüche, wobei die n keramischen Verbindungen S1, ..., S n alle identisch mit den p keramischen Verbindungen L1, ..., L p sind; wobei vorzugsweise sowohl n als auch p gleich 1 ist und die keramischen Verbindungen S1 und L1 beide Mullit sind.
  5. Verfahren nach einem der vorangehenden Ansprüche, wobei
    - die Einspritzung der Feststoffteilchen der n keramischen Verbindungen S1, ..., S n unter einem Winkel αS erfolgt, den von der Richtungen der Neigungsachse des Einspritzmittels für die Feststoffteilchen der n keramischen Verbindungen S1, ..., S n und der Längsachse des thermischen Strahls gebildet ist und der zwischen 75 und 105 Grad (°) beträgt; und
    - die Einspritzung der flüssigen Phase unter einem Winkel αL erfolgt, den von der Richtungen der Neigungsachse des Einspritzmittels für die flüssige Phase und der Längsachse des thermischen Strahls gebildet ist und der zwischen 75° und 105° beträgt.
  6. Verfahren nach einem der vorangehenden Ansprüche, wobei die flüssige Phase mit einem Abstand vom Substrat in den thermischen Strahl eingespritzt wird, der kleiner oder gleich dem Abstand vom Substrat ist, mit dem die Feststoffteilchen der n keramischen Verbindungen S1, ..., S n in den thermischen Strahl eingespritzt werden.
  7. Verfahren nach einem der vorangehenden Ansprüche, wobei die Abscheidung der Schicht durch ein Geblasenebogenplasmaspritzverfahren unter Verwendung eines Plasmagases erfolgt; wobei vorzugsweise das Plasmagas ausgewählt ist aus Argon, Helium, Distickstoff, Dihydrogen, binären Gemischen davon, wie etwa einem Argon-Helium-Gemisch oder einem Argon-Dihydrogen-Gemisch, und ternären Gemischen davon, wie etwa einem ternären Argon-Helium-Dihydrogen-Gemisch.
  8. Verfahren nach einem der vorangehenden Ansprüche, wobei die oder jede der Schichten, die zumindest eine keramische Verbindung enthalten, eine Dicke von 10 µm bis 2 mm aufweist; und/oder der Volumenanteil der Feststoffteilchen der p keramischen Verbindungen L1, ..., L p und/oder der Vorläufer dieser keramischen Verbindungen in der flüssigen Phase 2 % bis 20 % beträgt; und/oder das Verhältnis des Volumens der Feststoffteilchen der n keramischen Verbindungen S1, ..., S n zum Volumen der Feststoffteilchen der p keramischen Verbindungen L1, ..., L p in einem Bereich von 0,4 bis 3 liegt; und/oder der Durchfluss, mit dem die flüssige Phase in den thermischen Strahl eingespritzt wird, 0,05 ± 0,03 Liter pro Minute (L/min) beträgt.
  9. Verfahren nach einem der vorangehenden Ansprüche, wobei die oder jede der Schichten, die zumindest eine keramische Verbindung enthalten, eine Porosität von zumindest 20%, vorzugsweise zumindest 20% und höchstens 40% aufweist; wobei die Porosität durch Messung des hydrostatischen Auftriebs gemäß der Norm NF EN 623-2 bestimmt wird.
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US20150329954A1 (en) 2015-11-19
FR2999457A1 (fr) 2014-06-20
WO2014095887A1 (fr) 2014-06-26
EP2935641A1 (de) 2015-10-28
ES2825054T3 (es) 2021-05-14
FR2999457B1 (fr) 2015-01-16

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