EP1184479A1 - Method of forming a reactive-element containing aluminide on a metallic substrate - Google Patents

Method of forming a reactive-element containing aluminide on a metallic substrate Download PDF

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Publication number
EP1184479A1
EP1184479A1 EP01402232A EP01402232A EP1184479A1 EP 1184479 A1 EP1184479 A1 EP 1184479A1 EP 01402232 A EP01402232 A EP 01402232A EP 01402232 A EP01402232 A EP 01402232A EP 1184479 A1 EP1184479 A1 EP 1184479A1
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EP
European Patent Office
Prior art keywords
coating
substrate
aluminide
reactive element
powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP01402232A
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German (de)
French (fr)
Inventor
Yann Jaslier
Alain Martinez
Marie-Christine Ntsama Etoundi
Guillaume Oberlaender
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Safran Aircraft Engines SAS
Original Assignee
SNECMA Moteurs SA
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Publication date
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Publication of EP1184479A1 publication Critical patent/EP1184479A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
    • C23C10/34—Embedding in a powder mixture, i.e. pack cementation
    • C23C10/52—Embedding in a powder mixture, i.e. pack cementation more than one element being diffused in one step
    • 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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/02—Pretreatment of the material to be coated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12528—Semiconductor component

Definitions

  • the invention relates to formation on a metal substrate.
  • an aluminide type protective coating incorporating at least one reactive element.
  • the field of application of the invention is that of production or repair of metal parts which, due to their use at high temperatures and in an oxidizing environment, must be provided with a protective coating.
  • the invention is particularly, but not exclusively, applicable to parts of gas turbines, in particular parts of parts turbojet engines.
  • Parts exposed to these temperatures are usually made of refractory metallic alloy, or superalloy, nickel-based or cobalt.
  • aluminide type coatings which allow in particular the development of a protective alumina film on their surface, are commonly used.
  • Aluminum cementation is the most common technique commonly used to form aluminide type coatings. This technique usually involves placing the metal substrate in a closed enclosure containing a cement and to bring the assembly to a temperature generally between 900 ° C and 1150 ° C.
  • the aluminide type coatings can be used alone, or in combination with an external barrier coating thermal such as a ceramic coating.
  • the aluminide type coating constitutes a bonding layer between the substrate and the external coating, the attachment of the latter being favored by the presence of the alumina film forming an adhesion layer.
  • aluminide alumina film In order to increase the service life of the generator aluminide alumina film and limit deterioration of the latter by flaking it is known to incorporate in the aluminide type coating at least one reactive element usually chosen from the group consisting of zirconium, yttrium, hafnium and lanthanides.
  • Such a reactive element reinforces the barrier function of diffusion towards elements of the metallic substrate susceptible affect the alumina film, and therefore promotes the integrity and persistence of this one.
  • the presence of the reactive element also results in a decrease in the rate of oxidation of the metal substrate and by a prevention of highly undesirable segregation of sulfur to interface with an external ceramic coating.
  • a first type of known process consists in combining or associating separately the reactive element with one or more constituents of the coating and to form it by a process of physical deposition on the metallic substrate.
  • a second type of known process consists in forming a aluminum coating incorporating a reactive element by chemical deposition in the gas phase (CVD).
  • CVD gas phase
  • a heat treatment allows reduction of oxide by aluminum.
  • a third known type of process uses the technique of aluminization, but by modifying it by incorporating the reactive element in the cement.
  • the object of the invention is to propose a method making it possible to simple and economical way the formation of a type coating aluminide incorporating at least one reactive element, on a substrate metallic.
  • the supply of the reactive element in the form of an oxide powder of this element makes it possible to avoid difficulties in handling the powder of reactive element.
  • the contribution of the reactive element to the surface of the metal substrate can be produced by coating with a composition containing the powder mixed with a liquid, or by spraying such a composition, or by projection of the powder on the substrate so that it becomes encrusted on its surface, or by electrophoresis.
  • the method according to the invention is remarkable in that, in despite the provision of the reactive element in powder form, a aluminide type coating is obtained having a microstructure and a effectiveness quite comparable to that of similar coatings of the prior art, while the method of implementing the method turns out particularly advantageous.
  • the reactive element is also brought as close as possible to the substrate. metallic, which optimizes the yield between mass of reactive element putting into play and doping of the coating thus produced.
  • the method makes it possible to bring the reactive element in localized regions of the substrate surface, for example at to repair a protective coating, which is not possible with the prior art methods in which the reactive element is deposited in the gas phase or incorporated into a cement.
  • the aluminide type coating can be formed by aluminization after addition of the reactive element to the surface of the substrate. No changes to known aluminization processes, except possibly the duration, is not necessary, which constitutes another another advantage of the process.
  • the aluminide type coating can be formed by deposition of coating components after addition of the reactive element on the surface of the substrate, and heat treatment to react the constituents between them.
  • the surface of the metal substrate at least aluminum in powder form and one then forms the aluminide type coating by heat treatment.
  • the reactive element and the aluminum can be brought to the surface of the substrate by coating or spraying with a liquid composition comprising a powder of the reactive element in oxide form, a aluminum powder and a binder, the coating or spraying being carried out advantageously in superimposed layers to reach a thickness depending on that of the desired aluminide type coating.
  • one carries out in in addition to the surface of the substrate a deposit of at least one metal chosen from the group consisting of platinum, palladium, rhodium and ruthenium.
  • the aluminide type coating formed by the process according to the invention can be used alone, or as a barrier underlay thermal, an external ceramic coating then being formed which anchors on an alumina film generated at the interface between the coating of aluminide type and external ceramic coating.
  • the invention also relates to metallic substrates, in particular gas turbine parts made of superalloy, fitted with aluminide type as obtained by the above process.
  • the process according to the invention is intended more particularly, but not only to the production of protective coatings of the type aluminide on metallic substrates in superalloy, in particular in nickel or cobalt-based superalloy, such as metallic substrates parts of gas turbines, in particular parts of turbojets.
  • At least one element reagent to be present in the aluminide type coating is brought to the surface of the substrate, prior to the formation of the coating, in the form of an oxide powder of the reactive element.
  • the reactive element is preferably chosen from zirconium, yttrium, hafnium and lanthanides.
  • the deposition in the form of oxide powder makes it possible to avoid difficulties in handling these reactive elements in contact with air.
  • a first technique consists in preparing a composition containing powder and liquid and coating the surface of the substrate metallic, or a selected part of this surface with this composition.
  • the liquid used is for example a resin, possibly added with a solvent which, after possible polymerization of the resin, allows to fix the powder on the surface.
  • the coating can be very conventionally performed with a brush.
  • composition containing the powder and a liquid can be sprayed onto the surface or onto a selected part of it.
  • Another usable technique is to spray the powder alone on the surface of the substrate, or on a selected part thereof.
  • the projection is carried out by giving the powder particles a sufficient energy for them to become encrusted on the surface of the substrate.
  • Yet another technique is to deposit the powder in the substrate surface by electrophoresis. This is a good technique known per se, a brief description of which can be found in the document FR 96 15257 already cited.
  • a possible initial step in the process can consist in the formation on the surface of the substrate of a coating in one precious metal chosen from platinum, palladium, rhodium and ruthenium.
  • a metallic coating can be carried out by sputtering or by electrolytic deposition, a diffusion heat treatment is then often carried out.
  • a platinum group metal coating could be produced after the active element oxide powder has been added to the surface of the substrate.
  • the next step in the process is to form the coating of aluminide type.
  • a conventional process is implemented aluminization by cementation.
  • Case hardening in pack with contact between a case hardening powder and the substrate consists in burying the latter in a powder containing (i) an aluminum alloy, generally a chromium-aluminum alloy, (ii) an inert constituent, such as alumina, to avoid sintering, and (iii) a halogenated activator (for example NH 4 Cl, NH 4 F, AlF 3 , NaF, NaCl, ...) which allows the transport of the metal to be deposited between the cement and the substrate.
  • the whole is brought to a temperature of, for example, between 900 ° C. and 1150 ° C. in an oven.
  • Case hardening can also be carried out without contact with the substrate, the cement being placed apart in the furnace.
  • the halogenated activator can be incorporated into the cement or be brought separately in the oven.
  • the reactive element oxide previously brought to the surface of the substrate can be at least partially reduced.
  • the oxide is dispersed in a resin, the latter is degraded quickly by the halides formed by the activating element and by the heat.
  • Thermochemical reactions occur between halides, cement, reactive element oxide and the metal alloy of substrate which allow the formation of the aluminide coating and the dispersion of the reactive element within the aluminide coating formed.
  • a nickel-based superalloy substrate With a nickel-based superalloy substrate, a nickel aluminide containing the reactive element.
  • Processes other than aluminization can be used to form the aluminide type coating.
  • constituents of the desired coating on the substrate by physical gas deposition process, such as sputtering cathodic or plasma projection, or chemical deposition processes in the gas phase from gaseous precursors. These processes are known in themselves. We could for example refer to the documents GB 2 005 729, US 5 741 604 and US 5 494 704. The deposit of the constituents can be made in alternating overlapping layers.
  • a treatment thermal provides the desired aluminide with reduction any oxide previously brought to the surface of the substrate and dispersion of the reactive element released within the coating.
  • a mixed deposit of powder of reactive element oxide and aluminum powder is produced on the surface of the metal substrate.
  • the deposit can be made by coating or spraying with a composition containing the oxide powder, the aluminum powder and an inorganic or organic binder, such as a resin possibly diluted in a solvent.
  • Several overlapping layers are formed according to the thickness of the coating to be produced.
  • a heat treatment is then carried out at a temperature of preferably between 800 ° C and 1100 ° C to allow the formation of a aluminide by diffusion from the metal substrate, and the dispersion of the reactive element within the coating.
  • the metal substrate can be used with the only coating aluminide forming a protective coating against corrosion and oxidation at high temperatures.
  • an external coating in ceramic for example zirconia, yttrium oxide or zirconia yttria.
  • This external coating obtained by a physical deposition process such as, for example, sputtering, thermal spraying, evaporation under an electron beam, constitutes a thermal barrier.
  • the aluminide type intermediate coating then in particular has a bonding layer function allowing, via a developed alumina film on its surface, the attachment of the external ceramic coating.
  • a nickel-based superalloy metal substrate was provided a coating of nickel aluminide doped with zirconium in the way next.
  • a zirconia powder of average particle size equal to 14 ⁇ m was mixed with a liquid acrylate resin at a rate of 1 part by weight of powder for 8 parts by weight of resin. The mixture was applied to the substrate by coating with a brush then the resin been polymerized by UV exposure.
  • Non-contact cementation aluminization was then carried out by placing the substrate in an oven in the presence of a cement and an activator.
  • the cement was composed of 30% by weight of aluminum and 70% by weight of chromium, and the activator used was NH 4 Cl.
  • the aluminization was carried out at a temperature of approximately 1100 ° C. for a period of 4 h 30 min approximately.
  • the acrylate resin was rapidly degraded by the halides formed and the heat, while the zirconia was reduced.
  • a nickel-based superalloy substrate was thus obtained with a nickel aluminide coating containing 0.9% by mass of zirconium.
  • a nickel-based superalloy metal substrate was subjected to sandblasting with a zirconia powder identical to that of Example 1.
  • the sanding allowed the inlay and the surface deposition of the substrate of zirconia particles.
  • a contactless cementation aluminization was then carried out as in Example 1.
  • the nickel aluminide obtained has a zirconium content of a few hundred ppm, as well as a fine dispersion of alumina particles with a particle size of less than one micron.
  • a nickel-based superalloy metal substrate was coated with several layers of aluminizing paint.
  • This painting was consisting of the dispersion in an inorganic binder of a mixture of zirconia powder, aluminum powder and silicon powder in respective weight proportions of 8%, 82% and 10%.
  • the layers were formed by spraying paint and deposited successively with intermediate air drying supplemented by a steaming at 90 ° C for 30 min. The number of layers was chosen in depending on the thickness of the desired aluminide coating.
  • the metal substrate was then placed in an oven to undergo a heat treatment at 1000 ° C under a neutral atmosphere (argon).
  • a nickel aluminide coating was obtained by diffusion in which of the zirconium was dispersed.
  • the deposition of reactive element oxide by coating or spraying is advantageous in that it makes it possible to form this deposit on only part of the surface of the metal substrate. We then chooses the most exposed critical parts of the substrate, or the parts of the substrate that require repair of the coating aluminide type and any external ceramic coating.
  • the method can be implemented so similar with yttrium oxide powder, oxide powder hafnium, lanthanide oxide powder, or a mixture of two or more of these powders.

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

L'élément réactif est apporté à la surface du substrat métallique sous forme de poudre d'oxyde et on forme ensuite le revêtement de type aluminiure.The reactive element is brought to the surface of the metallic substrate in the form of oxide powder and the coating of the aluminide type is then formed.

Description

L'invention concerne la formation sur un substrat métallique d'un revêtement de protection de type aluminiure incorporant au moins un élément réactif.The invention relates to formation on a metal substrate. an aluminide type protective coating incorporating at least one reactive element.

Le domaine d'application de l'invention est celui de la réalisation ou de la réfection de pièces métalliques qui, du fait de leur utilisation à des températures élevées et en milieu oxydant, doivent être munies d'un revêtement de protection.The field of application of the invention is that of production or repair of metal parts which, due to their use at high temperatures and in an oxidizing environment, must be provided with a protective coating.

L'invention est notamment, mais non exclusivement, applicable à des pièces de turbines à gaz, en particulier des pièces de parties chaudes de turboréacteurs.The invention is particularly, but not exclusively, applicable to parts of gas turbines, in particular parts of parts turbojet engines.

Afin d'optimiser leur fonctionnement, on cherche à faire fonctionner des turbines à gaz, notamment des turboréacteurs, aux températures les plus élevées possibles.In order to optimize their operation, we seek to make operate gas turbines, particularly turbojets, highest possible temperatures.

Les pièces exposées à ces températures sont habituellement réalisées en alliage métallique réfractaire, ou superalliage, à base nickel ou cobalt.Parts exposed to these temperatures are usually made of refractory metallic alloy, or superalloy, nickel-based or cobalt.

Pour améliorer leur tenue aux températures élevées, en particulier leur résistance à la corrosion et à l'oxydation, il est bien connu de former un revêtement de protection sur le substrat métallique en superalliage.To improve their resistance to high temperatures, particularly their resistance to corrosion and oxidation, it is well known to form a protective coating on the metal substrate by superalloy.

Parmi les matériaux constitutifs d'un tel revêtement de protection, les revêtements de type aluminiure qui permettent notamment le développement d'un film d'alumine protecteur à leur surface, sont couramment utilisés.Among the materials constituting such a coating of protection, aluminide type coatings which allow in particular the development of a protective alumina film on their surface, are commonly used.

L'aluminisation par cémentation est la technique la plus couramment utilisée pour former les revêtements de type aluminiure. Cette technique consiste généralement à placer le substrat métallique dans une enceinte fermée contenant un cément et à porter l'ensemble à une température comprise généralement entre 900°C et 1150°C.Aluminum cementation is the most common technique commonly used to form aluminide type coatings. This technique usually involves placing the metal substrate in a closed enclosure containing a cement and to bring the assembly to a temperature generally between 900 ° C and 1150 ° C.

Les revêtements de type aluminiure peuvent être utilisés seuls, ou en combinaison avec un revêtement externe formant barrière thermique tel qu'un revêtement céramique. Dans ce dernier cas, le revêtement de type aluminiure constitue une couche de liaison entre le substrat et le revêtement externe, l'accrochage de ce dernier étant favorisé par la présence du film d'alumine formant couche d'adhésion.The aluminide type coatings can be used alone, or in combination with an external barrier coating thermal such as a ceramic coating. In the latter case, the aluminide type coating constitutes a bonding layer between the substrate and the external coating, the attachment of the latter being favored by the presence of the alumina film forming an adhesion layer.

Afin d'augmenter la durée de vie de l'aluminiure générateur du film d'alumine et de limiter la détérioration de ce dernier par écaillage, il est connu d'incorporer dans le revêtement de type aluminiure au moins un élément réactif choisi habituellement dans le groupe constitué par le zirconium, l'yttrium, l'hafnium et les lanthanides.In order to increase the service life of the generator aluminide alumina film and limit deterioration of the latter by flaking it is known to incorporate in the aluminide type coating at least one reactive element usually chosen from the group consisting of zirconium, yttrium, hafnium and lanthanides.

Un tel élément réactif renforce la fonction de barrière de diffusion vis-à-vis d'éléments du substrat métallique susceptibles d'affecter le film d'alumine, et favorise donc l'intégrité et la persistance de celui-ci. La présence de l'élément réactif se traduit aussi par une diminution de la vitesse d'oxydation du substrat métallique et par un empêchement de la ségrégation - hautement indésirable - du soufre à l'interface avec un revêtement externe céramique.Such a reactive element reinforces the barrier function of diffusion towards elements of the metallic substrate susceptible affect the alumina film, and therefore promotes the integrity and persistence of this one. The presence of the reactive element also results in a decrease in the rate of oxidation of the metal substrate and by a prevention of highly undesirable segregation of sulfur to interface with an external ceramic coating.

Différents procédés ont été proposés pour former un revêtement de type aluminiure incorporant un élément réactif.Different methods have been proposed to form a aluminide type coating incorporating a reactive element.

Un premier type de procédé connu consiste à allier ou associer séparément l'élément réactif avec un ou plusieurs constituants du revêtement et à former celui-ci par un processus de dépôt physique sur le substrat métallique.A first type of known process consists in combining or associating separately the reactive element with one or more constituents of the coating and to form it by a process of physical deposition on the metallic substrate.

On pourra par exemple se référer au document US 4 055 705 qui décrit la formation d'une couche de liaison par projection plasma, frittage ou autre technique physique de dépôt de NiCrAIY. On pourra aussi se référer au document FR 96 15257 qui décrit le dépôt par électrophorèse, ou sous forme d'une peinture avec liant thermodégradable ou volatil, d'une poudre d'alliage MCrAIY (M étant Ni et/ou Co et/ou Fe) sur un substrat métallique. Un dépôt électrolytique d'un alliage contenant un métal du groupe du platine est ensuite effectué avant traitement thermique et une éventuelle aluminisation. On pourra aussi se référer au document US 5 824 423 qui, bien qu'envisageant un dépôt initial d'élément réactif sur un substrat métallique par dépôt physique en phase gazeuse suivi d'aluminisation, indique, de préférence, la formation d'une couche de liaison par projection plasma d'une poudre pré-alliée MAIY (M étant Ni et/ou Co et/ou Fe). We can for example refer to document US 4,055,705 which describes the formation of a bonding layer by plasma projection, sintering or other physical NiCrAIY deposition technique. We can also refer to document FR 96 15257 which describes the deposition by electrophoresis, or in the form of a paint with thermodegradable binder or volatile, of an MCrAIY alloy powder (M being Ni and / or Co and / or Fe) on a metallic substrate. An electrolytic deposit of an alloy containing a platinum group metal is then made before treatment thermal and possible aluminization. We can also refer to document US 5,824,423 which, although considering an initial filing reactive element on a metallic substrate by physical phase deposition gas followed by aluminization, preferably indicates the formation of a bonding layer by plasma spraying of a MAIY pre-alloyed powder (M being Ni and / or Co and / or Fe).

Ces types de procédés connus requièrent une étape supplémentaire d'addition de l'élément réactif dans un alliage, ce qui peut nécessiter des investissements importants.These types of known processes require a step additional addition of the reactive element to an alloy, which can require significant investment.

On pourra encore se référer aux documents SU 1 527 320 et SU 541 896 qui décrivent l'application à la surface d'un substrat métallique d'une suspension contenant des poudres d'aluminium et de zirconium et un liant, tel qu'un vernis en solution, pour obtenir un revêtement de protection après séchage et traitement thermique.We can also refer to documents SU 1 527 320 and SU 541 896 which describe the application to the surface of a metallic substrate a suspension containing aluminum and zirconium powders and a binder, such as a solution varnish, to obtain a coating of protection after drying and heat treatment.

Mais la manipulation d'éléments tels que le zirconium sous forme divisée est particulièrement délicate en raison des risques importants de réaction spontanée avec l'air.But the manipulation of elements such as zirconium under divided form is particularly delicate due to the risks important spontaneous reaction with air.

Un deuxième type de procédé connu consiste à former un revêtement aluminium incorporant un élément réactif par dépôt chimique en phase gazeuse (CVD). On pourra se référer au document US 5 503 874 qui décrit le dépôt alterné d'une couche d'aluminium et d'une couche d'oxyde métallique, tel qu'oxyde d'yttrium, de zirconium, de chrome ou d'hafnium, à partir de précurseurs organométalliques. Un traitement thermique permet la réduction de l'oxyde par l'aluminium. On pourra aussi se référer au document US 5 989 733 qui décrit la formation d'un revêtement par dépôt chimique en phase gazeuse d'éléments Al, Si, Hf, et éventuellement Zr ou autre élément réactif précédé ou suivi d'électrodéposition de Pt, pour obtenir un aluminiure de nickel modifié.A second type of known process consists in forming a aluminum coating incorporating a reactive element by chemical deposition in the gas phase (CVD). We can refer to the document US 5,503,874 which describes the alternate deposition of a layer of aluminum and a layer of metal oxide, such as yttrium oxide, zirconium, chromium or hafnium, from organometallic precursors. A heat treatment allows reduction of oxide by aluminum. We may also refer to document US 5,989,733 which describes the training a coating by chemical vapor deposition of Al, Si elements, Hf, and possibly Zr or other reactive element preceded or followed Pt electrodeposition to obtain a modified nickel aluminide.

Ces types de procédés connus requièrent l'utilisation d'une installation de dépôt chimique en phase gazeuse coûteuse en investissements et en maintenance.These types of known methods require the use of a costly gas phase chemical deposition facility investments and maintenance.

Un troisième type de procédé connu fait appel à la technique d'aluminisation, mais en la modifiant par incorporation de l'élément réactif dans le cément. On pourra se référer au document FR 2 511 396 qui propose l'utilisation d'un cément contenant de l'aluminium, un alliage d'aluminium, un sel activateur et un élément réactif.A third known type of process uses the technique of aluminization, but by modifying it by incorporating the reactive element in the cement. Reference may be made to document FR 2 511 396 which proposes the use of a cement containing aluminum, an alloy aluminum, an activating salt and a reactive element.

Objet et résumé de l'inventionSubject and summary of the invention

L'invention a pour but de proposer un procédé permettant de façon simple et économique la formation d'un revêtement de type aluminiure incorporant au moins un élément réactif, sur un substrat métallique. The object of the invention is to propose a method making it possible to simple and economical way the formation of a type coating aluminide incorporating at least one reactive element, on a substrate metallic.

Ce but est atteint du fait que, selon l'invention, le procédé comprend les étapes qui consistent à :

  • apporter ledit élément réactif à la surface du substrat métallique sous forme de poudre d'oxyde de l'élément réactif, et
  • former ensuite le revêtement de type aluminiure.
This object is achieved because, according to the invention, the method comprises the steps which consist in:
  • bringing said reactive element to the surface of the metal substrate in the form of oxide powder of the reactive element, and
  • then form the aluminide type coating.

L'apport de l'élément réactif sous forme d'une poudre d'oxyde de cet élément permet d'éviter des difficultés de manipulations de poudre d'élément réactif.The supply of the reactive element in the form of an oxide powder of this element makes it possible to avoid difficulties in handling the powder of reactive element.

L'apport de l'élément réactif à la surface du substrat métallique peut être réalisé par enduction avec une composition contenant la poudre mélangée à un liquide, ou par projection d'une telle composition, ou par projection de la poudre sur le substrat pour qu'elle s'incruste à sa surface, ou encore par électrophorèse.The contribution of the reactive element to the surface of the metal substrate can be produced by coating with a composition containing the powder mixed with a liquid, or by spraying such a composition, or by projection of the powder on the substrate so that it becomes encrusted on its surface, or by electrophoresis.

Le procédé selon l'invention est remarquable en ce que, en dépit de l'apport de l'élément réactif sous forme pulvérulente, un revêtement de type aluminiure est obtenu ayant une microstructure et une efficacité tout à fait comparables à celles des revêtements analogues de l'art antérieur, alors que le mode de mise en oeuvre du procédé s'avère particulièrement avantageux.The method according to the invention is remarkable in that, in despite the provision of the reactive element in powder form, a aluminide type coating is obtained having a microstructure and a effectiveness quite comparable to that of similar coatings of the prior art, while the method of implementing the method turns out particularly advantageous.

En effet, le procédé ne nécessite pas d'équipements coûteux à réaliser ou à entretenir.Indeed, the process does not require expensive equipment to to build or maintain.

L'élément réactif est en outre amené au plus près du substrat métallique, ce qui optimise le rendement entre masse d'élément réactif mise en jeu et dopage du revêtement ainsi réalisé.The reactive element is also brought as close as possible to the substrate. metallic, which optimizes the yield between mass of reactive element putting into play and doping of the coating thus produced.

De plus, il est possible de contrôler précisément la masse d'élément réactif amenée et ce dans une très large plage.In addition, it is possible to precisely control the mass of reactive element supplied and this over a very wide range.

De plus encore, le procédé permet d'amener l'élément réactif dans des régions localisées de la surface du substrat, par exemple aux fins de réparation d'un revêtement de protection, ce qui n'est pas possible avec les procédés de l'art antérieur dans lesquels l'élément réactif est déposé en phase gazeuse ou incorporé dans un cément.Furthermore, the method makes it possible to bring the reactive element in localized regions of the substrate surface, for example at to repair a protective coating, which is not possible with the prior art methods in which the reactive element is deposited in the gas phase or incorporated into a cement.

Le revêtement de type aluminiure peut être formé par aluminisation après apport de l'élément réactif à la surface du substrat. Aucune modification des processus connus d'aluminisation, si ce n'est éventuellement la durée, n'est nécessaire, ce qui constitue encore un autre avantage du procédé. The aluminide type coating can be formed by aluminization after addition of the reactive element to the surface of the substrate. No changes to known aluminization processes, except possibly the duration, is not necessary, which constitutes another another advantage of the process.

En variante, l'on peut former le revêtement de type aluminiure par dépôt de constituants du revêtement après apport de l'élément réactif à la surface du substrat, et traitement thermique pour faire réagir les constituants entre eux.Alternatively, the aluminide type coating can be formed by deposition of coating components after addition of the reactive element on the surface of the substrate, and heat treatment to react the constituents between them.

Toujours en variante, l'on apporte en outre à la surface du substrat métallique au moins de l'aluminium sous forme de poudre et l'on forme ensuite le revêtement de type aluminiure par traitement thermique. L'élément réactif et l'aluminium peuvent être amenés à la surface du substrat par enduction ou projection avec une composition liquide comprenant une poudre de l'élément réactif sous forme oxyde, une poudre d'aluminium et un liant, l'enduction ou la projection étant réalisée avantageusement en couches superposées pour atteindre une épaisseur fonction de celle du revêtement de type aluminiure désiré.Still in a variant, the surface of the metal substrate at least aluminum in powder form and one then forms the aluminide type coating by heat treatment. The reactive element and the aluminum can be brought to the surface of the substrate by coating or spraying with a liquid composition comprising a powder of the reactive element in oxide form, a aluminum powder and a binder, the coating or spraying being carried out advantageously in superimposed layers to reach a thickness depending on that of the desired aluminide type coating.

Selon encore une autre variante du procédé, l'on réalise en outre à la surface du substrat un dépôt d'au moins un métal choisi dans le groupe constitué par le platine, le palladium, le rhodium et le ruthénium.According to yet another variant of the method, one carries out in in addition to the surface of the substrate a deposit of at least one metal chosen from the group consisting of platinum, palladium, rhodium and ruthenium.

Le revêtement de type aluminiure formé par le procédé selon l'invention peut être utilisé seul, ou comme sous-couche de barrière thermique, un revêtement externe en céramique étant alors formé qui s'ancre sur un film d'alumine généré à l'interface entre le revêtement de type aluminiure et le revêtement externe céramique.The aluminide type coating formed by the process according to the invention can be used alone, or as a barrier underlay thermal, an external ceramic coating then being formed which anchors on an alumina film generated at the interface between the coating of aluminide type and external ceramic coating.

L'invention vise aussi des substrats métalliques, notamment des pièces de turbine à gaz en superalliage, munis de revêtements de type aluminiure tels qu'obtenus par le procédé ci-dessus.The invention also relates to metallic substrates, in particular gas turbine parts made of superalloy, fitted with aluminide type as obtained by the above process.

L'invention sera mieux comprise à la lecture de la description détaillée faite ci-après à titre indicatif, mais non limitatif.The invention will be better understood on reading the description detailed below for information, but not limitative.

Description détaillée de modes de réalisationDetailed description of embodiments

Le procédé selon l'invention est destiné plus particulièrement, mais non seulement, à la réalisation de revêtements protecteurs de type aluminiure sur des substrats métalliques en superalliage, notamment en superalliage à base nickel ou cobalt, tels que des substrats métalliques de pièces de turbines à gaz, en particulier de pièces de turboréacteurs.The process according to the invention is intended more particularly, but not only to the production of protective coatings of the type aluminide on metallic substrates in superalloy, in particular in nickel or cobalt-based superalloy, such as metallic substrates parts of gas turbines, in particular parts of turbojets.

Selon une caractéristique de l'invention, au moins un élément réactif devant être présent dans le revêtement de type aluminiure est apporté à la surface du substrat, préalablement à la formation du revêtement, sous forme d'une poudre d'oxyde de l'élément réactif.According to a characteristic of the invention, at least one element reagent to be present in the aluminide type coating is brought to the surface of the substrate, prior to the formation of the coating, in the form of an oxide powder of the reactive element.

L'élément réactif est choisi de préférence parmi le zirconium, l'yttrium, l'hafnium et les lanthanides.The reactive element is preferably chosen from zirconium, yttrium, hafnium and lanthanides.

Le dépôt sous forme de poudre d'oxyde permet d'éviter des difficultés de manipulation de ces éléments réactifs au contact de l'air.The deposition in the form of oxide powder makes it possible to avoid difficulties in handling these reactive elements in contact with air.

Plusieurs techniques simples peuvent être utilisées pour le dépôt de la poudre d'oxyde à la surface du substrat.Several simple techniques can be used to deposition of the oxide powder on the surface of the substrate.

Une première technique consiste à préparer une composition contenant la poudre et un liquide et à enduire la surface du substrat métallique, ou une partie sélectionnée de cette surface avec cette composition. Le liquide utilisé est par exemple une résine, éventuellement additionnée d'un solvant ce qui, après éventuelle polymérisation de la résine, permet de fixer la poudre sur la surface. L'enduction peut être très classiquement réalisée au pinceau.A first technique consists in preparing a composition containing powder and liquid and coating the surface of the substrate metallic, or a selected part of this surface with this composition. The liquid used is for example a resin, possibly added with a solvent which, after possible polymerization of the resin, allows to fix the powder on the surface. The coating can be very conventionally performed with a brush.

En variante, une telle composition contenant la poudre et un liquide peut être projetée sur la surface ou sur une partie sélectionnée de celle-ci.Alternatively, such a composition containing the powder and a liquid can be sprayed onto the surface or onto a selected part of it.

Une autre technique utilisable consiste à projeter la poudre seule sur la surface du substrat, ou sur une partie sélectionnée de celle-ci. La projection est réalisée en conférant aux particules de poudre une énergie suffisante pour qu'elles puissent s'incruster à la surface du substrat.Another usable technique is to spray the powder alone on the surface of the substrate, or on a selected part thereof. The projection is carried out by giving the powder particles a sufficient energy for them to become encrusted on the surface of the substrate.

Encore une autre technique consiste à déposer la poudre à la surface du substrat par électrophorèse. Il s'agit d'une technique bien connue en soi dont une rapide description peut être trouvée dans le document FR 96 15257 déjà cité.Yet another technique is to deposit the powder in the substrate surface by electrophoresis. This is a good technique known per se, a brief description of which can be found in the document FR 96 15257 already cited.

On notera que, avant amenée de la poudre d'oxyde à la surface du substrat, une étape initiale éventuelle du procédé peut consister dans la formation à la surface du substrat d'un revêtement en un métal précieux choisi parmi le platine, le palladium, le rhodium et le ruthénium. De façon connue en soi, un tel revêtement métallique peut être réalisé par pulvérisation cathodique ou par dépôt électrolytique, un traitement thermique de diffusion étant ensuite souvent réalisé. En variante, un tel revêtement par un métal du groupe du platine pourrait être réalisé après apport de la poudre d'oxyde d'élément actif à la surface du substrat.It will be noted that, before bringing the oxide powder to the substrate surface, a possible initial step in the process can consist in the formation on the surface of the substrate of a coating in one precious metal chosen from platinum, palladium, rhodium and ruthenium. In a manner known per se, such a metallic coating can be carried out by sputtering or by electrolytic deposition, a diffusion heat treatment is then often carried out. In alternatively, such a platinum group metal coating could be produced after the active element oxide powder has been added to the surface of the substrate.

L'étape suivante du procédé consiste à former le revêtement de type aluminiure.The next step in the process is to form the coating of aluminide type.

Avantageusement, on met en oeuvre un processus classique d'aluminisation par cémentation.Advantageously, a conventional process is implemented aluminization by cementation.

La cémentation en pack avec contact entre une poudre de cémentation et le substrat consiste à enfouir celui-ci dans une poudre contenant (i) un alliage de l'aluminium, généralement un alliage chrome-aluminium, (ii) un constituant inerte, tel que l'alumine, pour éviter le frittage, et (iii) un activateur halogéné (par exemple NH4Cl, NH4F, AlF3, NaF, NaCl, ...) qui permet le transport du métal à déposer entre le cément et le substrat. L'ensemble est porté à une température comprise par exemple entre 900°C et 1150°C dans un four.Case hardening in pack with contact between a case hardening powder and the substrate consists in burying the latter in a powder containing (i) an aluminum alloy, generally a chromium-aluminum alloy, (ii) an inert constituent, such as alumina, to avoid sintering, and (iii) a halogenated activator (for example NH 4 Cl, NH 4 F, AlF 3 , NaF, NaCl, ...) which allows the transport of the metal to be deposited between the cement and the substrate. The whole is brought to a temperature of, for example, between 900 ° C. and 1150 ° C. in an oven.

La cémentation peut aussi être réalisée sans contact avec le substrat, le cément étant disposé à part dans le four. Dans ce dernier cas, l'activateur halogéné peut être incorporé au cément ou être amené séparément dans le four.Case hardening can also be carried out without contact with the substrate, the cement being placed apart in the furnace. In this last case, the halogenated activator can be incorporated into the cement or be brought separately in the oven.

Lors de l'aluminisation, l'oxyde d'élément réactif préalablement amené à la surface du substrat peut être au moins partiellement réduit. Lorsque l'oxyde est dispersé dans une résine, cette dernière est dégradée rapidement par les halogénures formés par l'élément activateur et par la chaleur.During aluminization, the reactive element oxide previously brought to the surface of the substrate can be at least partially reduced. When the oxide is dispersed in a resin, the latter is degraded quickly by the halides formed by the activating element and by the heat.

Des réactions thermochimiques se produisent entre les halogénures, le cément, l'oxyde d'élément réactif et l'alliage métallique du substrat qui permettent la formation du revêtement aluminiure et la dispersion de l'élément réactif au sein du revêtement aluminiure formé. Avec un substrat en superalliage à base de nickel, on obtient un aluminiure de nickel contenant l'élément réactif.Thermochemical reactions occur between halides, cement, reactive element oxide and the metal alloy of substrate which allow the formation of the aluminide coating and the dispersion of the reactive element within the aluminide coating formed. With a nickel-based superalloy substrate, a nickel aluminide containing the reactive element.

Des processus autres que l'aluminisation peuvent être utilisés pour former le revêtement de type aluminiure. Par exemple, on pourra déposer des constituants du revêtement souhaité sur le substrat par des processus de dépôt physique en phase gazeuse, tel que pulvérisation cathodique ou projection au plasma, ou des processus de dépôt chimique en phase gazeuse à partir de précurseurs gazeux. Ces processus sont connus en eux-mêmes. On pourra par exemple se référer aux documents GB 2 005 729, US 5 741 604 et US 5 494 704. Le dépôt des constituants peut être réalisé en couches alternées superposées. Un traitement thermique permet d'obtenir l'aluminiure recherché avec réduction éventuelle de l'oxyde préalablement amené à la surface du substrat et dispersion de l'élément réactif libéré au sein du revêtement.Processes other than aluminization can be used to form the aluminide type coating. For example, we can deposit constituents of the desired coating on the substrate by physical gas deposition process, such as sputtering cathodic or plasma projection, or chemical deposition processes in the gas phase from gaseous precursors. These processes are known in themselves. We could for example refer to the documents GB 2 005 729, US 5 741 604 and US 5 494 704. The deposit of the constituents can be made in alternating overlapping layers. A treatment thermal provides the desired aluminide with reduction any oxide previously brought to the surface of the substrate and dispersion of the reactive element released within the coating.

Selon encore une autre variante, un dépôt mixte de poudre d'oxyde d'élément réactif et de poudre d'aluminium est réalisé sur la surface du substrat métallique. Le dépôt peut être réalisé par enduction ou projection avec une composition contenant la poudre d'oxyde, la poudre d'aluminium et un liant inorganique ou organique, tel qu'une résine éventuellement diluée dans un solvant. Plusieurs couches superposées sont formées en fonction de l'épaisseur du revêtement à réaliser. Un traitement thermique est ensuite réalisé à une température comprise de préférence entre 800°C et 1100°C pour permettre la formation d'un aluminiure par diffusion à partir du substrat métallique, et la dispersion de l'élément réactif au sein du revêtement.According to yet another variant, a mixed deposit of powder of reactive element oxide and aluminum powder is produced on the surface of the metal substrate. The deposit can be made by coating or spraying with a composition containing the oxide powder, the aluminum powder and an inorganic or organic binder, such as a resin possibly diluted in a solvent. Several overlapping layers are formed according to the thickness of the coating to be produced. A heat treatment is then carried out at a temperature of preferably between 800 ° C and 1100 ° C to allow the formation of a aluminide by diffusion from the metal substrate, and the dispersion of the reactive element within the coating.

Le substrat métallique peut être utilisé avec le seul revêtement en aluminiure formant revêtement de protection contre la corrosion et l'oxydation aux températures élevées.The metal substrate can be used with the only coating aluminide forming a protective coating against corrosion and oxidation at high temperatures.

Il est aussi possible d'ajouter un revêtement externe en céramique, par exemple en zircone, en oxyde d'yttrium ou en zircone yttriée. Ce revêtement externe, obtenu par un procédé de dépôt physique tel que, par exemple, pulvérisation cathodique, projection thermique, évaporation sous faisceau électronique, constitue une barrière thermique. Le revêtement intermédiaire de type aluminiure a alors notamment une fonction de couche de liaison permettant, via un film d'alumine développé à sa surface, l'accrochage du revêtement externe céramique.It is also possible to add an external coating in ceramic, for example zirconia, yttrium oxide or zirconia yttria. This external coating, obtained by a physical deposition process such as, for example, sputtering, thermal spraying, evaporation under an electron beam, constitutes a thermal barrier. The aluminide type intermediate coating then in particular has a bonding layer function allowing, via a developed alumina film on its surface, the attachment of the external ceramic coating.

Des exemples de mise en oeuvre du procédé seront maintenant décrits à titre indicatif mais non limitatif.Examples of implementation of the method will be now described for information but not limitation.

Exemple 1Example 1

Un substrat métallique en superalliage à base nickel a été muni d'un revêtement en aluminiure de nickel dopé au zirconium de la façon suivante.A nickel-based superalloy metal substrate was provided a coating of nickel aluminide doped with zirconium in the way next.

Une poudre de zircone de granulométrie moyenne égale à 14 µm a été mélangée avec une résine acrylate liquide à raison de 1 partie en poids de poudre pour 8 parties en poids de résine. Le mélange a été appliqué sur le substrat par enduction au pinceau puis la résine a été polymérisée par exposition UV.A zirconia powder of average particle size equal to 14 µm was mixed with a liquid acrylate resin at a rate of 1 part by weight of powder for 8 parts by weight of resin. The mixture was applied to the substrate by coating with a brush then the resin been polymerized by UV exposure.

Une aluminisation par cémentation sans contact a été ensuite réalisée en plaçant le substrat dans un four en présence d'un cément et d'un activateur. Le cément était composé de 30 % en poids d'aluminium et 70 % en poids de chrome, et l'activateur utilisé était du NH4Cl. L'aluminisation a été effectuée sous une température de 1100°C environ pendant une durée de 4 h 30 min environ. La résine acrylate a été rapidement dégradée par les halogénures formés et la chaleur, tandis que la zircone a été réduite.Non-contact cementation aluminization was then carried out by placing the substrate in an oven in the presence of a cement and an activator. The cement was composed of 30% by weight of aluminum and 70% by weight of chromium, and the activator used was NH 4 Cl. The aluminization was carried out at a temperature of approximately 1100 ° C. for a period of 4 h 30 min approximately. The acrylate resin was rapidly degraded by the halides formed and the heat, while the zirconia was reduced.

On a ainsi obtenu un substrat en superalliage à base nickel avec un revêtement en aluminiure de nickel contenant 0,9 % en masse de zirconium.A nickel-based superalloy substrate was thus obtained with a nickel aluminide coating containing 0.9% by mass of zirconium.

Exemple 2Example 2

Un substrat métallique en superalliage à base nickel a été soumis à un sablage avec une poudre de zircone identique à celle de l'exemple 1. Le sablage a permis l'incrustation et le dépôt en surface du substrat de particules de zircone.A nickel-based superalloy metal substrate was subjected to sandblasting with a zirconia powder identical to that of Example 1. The sanding allowed the inlay and the surface deposition of the substrate of zirconia particles.

Une aluminisation par cémentation sans contact a été ensuite réalisée comme dans l'exemple 1. L'aluminiure de nickel obtenu présente une teneur en zirconium de quelques centaines de ppm, ainsi qu'une fine dispersion de particules d'alumine de granulométrie inférieure au micron.A contactless cementation aluminization was then carried out as in Example 1. The nickel aluminide obtained has a zirconium content of a few hundred ppm, as well as a fine dispersion of alumina particles with a particle size of less than one micron.

Exemple 3Example 3

Un substrat métallique en superalliage à base nickel a été revêtu de plusieurs couches de peinture aluminisante. Cette peinture était constituée par la dispersion dans un liant inorganique d'un mélange de poudre de zircone, de poudre d'aluminium et de poudre de silicium dans des proportions en masse respectives de 8 %, 82 % et 10 %. Les couches ont été formées par projection de la peinture et déposées successivement avec séchage intermédiaire à l'air complété par un étuvage à 90°C pendant 30 min. Le nombre de couches a été choisi en fonction de l'épaisseur du revêtement en aluminiure désiré. A nickel-based superalloy metal substrate was coated with several layers of aluminizing paint. This painting was consisting of the dispersion in an inorganic binder of a mixture of zirconia powder, aluminum powder and silicon powder in respective weight proportions of 8%, 82% and 10%. The layers were formed by spraying paint and deposited successively with intermediate air drying supplemented by a steaming at 90 ° C for 30 min. The number of layers was chosen in depending on the thickness of the desired aluminide coating.

Le substrat métallique a été ensuite placé dans un four pour subir un traitement thermique à 1000°C sous atmosphère neutre (argon). On a obtenu par diffusion un revêtement en aluminiure de nickel dans lequel du zirconium était dispersé.The metal substrate was then placed in an oven to undergo a heat treatment at 1000 ° C under a neutral atmosphere (argon). A nickel aluminide coating was obtained by diffusion in which of the zirconium was dispersed.

Comme déjà indiqué, le dépôt d'oxyde d'élément réactif par enduction ou projection est avantageux en ce qu'il permet de former ce dépôt sur une partie seulement de la surface du substrat métallique. On choisit alors les parties critiques les plus exposées du substrat, ou alors les parties du substrat qui nécessitent une réfection du revêtement de type aluminiure et du revêtement céramique externe éventuel.As already indicated, the deposition of reactive element oxide by coating or spraying is advantageous in that it makes it possible to form this deposit on only part of the surface of the metal substrate. We then chooses the most exposed critical parts of the substrate, or the parts of the substrate that require repair of the coating aluminide type and any external ceramic coating.

Bien que l'on ait envisagé le dépôt d'une poudre de zircone dans les exemples ci-dessus, le procédé peut être mis en oeuvre de façon similaire avec une poudre d'oxyde d'yttrium, une poudre d'oxyde d'hafnium, une poudre d'oxyde de lanthanide, ou un mélange de deux ou plus de ces poudres.Although consideration has been given to depositing a zirconia powder in the examples above, the method can be implemented so similar with yttrium oxide powder, oxide powder hafnium, lanthanide oxide powder, or a mixture of two or more of these powders.

Claims (18)

Procédé pour la formation, sur un substrat métallique, d'un revêtement de protection de type aluminiure incorporant au moins un élément réactif,
caractérisé en ce qu'il comprend les étapes consistant à : apporter ledit élément réactif à la surface du substrat métallique sous forme de poudre d'oxyde de l'élément réactif, et former ensuite le revêtement de type aluminiure. Process for the formation, on a metallic substrate, of a protective coating of the aluminide type incorporating at least one reactive element,
characterized in that it comprises the steps consisting in: bringing said reactive element to the surface of the metal substrate in the form of oxide powder of the reactive element, and then form the aluminide type coating. Procédé selon la revendication 1, caractérisé en ce que l'apport à la surface du substrat métallique est réalisé par enduction avec une composition contenant la poudre en milieu liquide.Method according to claim 1, characterized in that the addition to the surface of the metal substrate is carried out by coating with a composition containing the powder in a liquid medium. Procédé selon la revendication 1, caractérisé en ce que l'apport à la surface du substrat métallique est réalisé par projection sur cette surface d'une composition contenant la poudre en milieu liquide.Method according to claim 1, characterized in that the addition to the surface of the metal substrate is carried out by spraying onto this surface a composition containing the powder in a liquid medium. Procédé selon la revendication 1, caractérisé en ce que l'apport à la surface du substrat métallique est réalisé par projection de la poudre pour qu'elle s'incruste dans cette surface.Method according to claim 1, characterized in that the addition to the surface of the metal substrate is carried out by spraying the powder so that it becomes encrusted in this surface. Procédé selon la revendication 1, caractérisé en ce que l'apport de poudre à la surface du substrat métallique est réalisé par électrophorèse.Method according to claim 1, characterized in that the addition of powder to the surface of the metal substrate is carried out by electrophoresis. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le revêtement de type aluminiure est formé par aluminisation.Method according to any one of Claims 1 to 5, characterized in that the aluminide type coating is formed by aluminization. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le revêtement de type aluminiure est formé par dépôt de constituants du revêtement après apport de l'élément réactif à la surface du substrat métallique et traitement thermique pour faire réagir les constituants entre eux et disperser l'élément réactif au sein du revêtement.Process according to any one of Claims 1 to 5, characterized in that the aluminide type coating is formed by depositing constituents of the coating after the reactive element has been brought to the surface of the metal substrate and heat treatment to react the constituents between them and dispersing the reactive element within the coating. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que l'on apporte en outre à la surface du substrat métallique au moins de l'aluminium sous forme pulvérulente et l'on forme le revêtement de type aluminiure par traitement thermique.Process according to any one of Claims 1 to 5, characterized in that at least aluminum is added to the surface of the metal substrate in powder form and the coating of the aluminide type is formed by heat treatment . Procédé selon la revendication 8, caractérisé en ce qu'au moins un élément réactif et de l'aluminium sont apportés à la surface du substrat métallique à partir d'une composition liquide comprenant une poudre d'oxyde de l'élément réactif, une poudre d'aluminium et un liant.Method according to claim 8, characterized in that at least one reactive element and aluminum are brought to the surface of the metallic substrate from a liquid composition comprising an oxide powder of the reactive element, a powder aluminum and a binder. Procédé selon la revendication 9, caractérisé en ce que l'on réalise le dépôt de la composition liquide à la surface du substrat métallique en plusieurs couches superposées pour atteindre une épaisseur fonction de celle du revêtement de type aluminiure désiré.Process according to claim 9, characterized in that the liquid composition is deposited on the surface of the metal substrate in several superimposed layers to reach a thickness depending on that of the coating of the desired aluminide type. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que l'on apporte à la surface du substrat métallique au moins un élément réactif choisi dans le groupe constitué par le zirconium, l'yttrium, l'hafnium et les lanthanides.Process according to any one of Claims 1 to 10, characterized in that at least one reactive element chosen from the group consisting of zirconium, yttrium, hafnium and lanthanides is added to the surface of the metal substrate . Procédé selon l'une quelconque des revendications 1 à 11, caractérisé en ce que l'on réalise en outre à la surface du substrat un dépôt d'au moins un métal choisi dans le groupe constitué par le platine, le palladium, le rhodium et le ruthénium.Process according to any one of Claims 1 to 11, characterized in that a deposit is also made on the surface of the substrate of at least one metal chosen from the group consisting of platinum, palladium, rhodium and ruthenium. Procédé selon l'une quelconque des revendications 1 à 12, caractérisé en ce que l'on forme un revêtement externe en céramique au-dessus du revêtement en aluminiure.Process according to any one of Claims 1 to 12, characterized in that an external ceramic coating is formed above the aluminide coating. Procédé selon l'une quelconque des revendications 1 à 13, caractérisé en ce que l'on forme le revêtement de type aluminure sur des zones localisées de la surface d'un substrat métallique aux fins de réparation d'un revêtement de protection du substrat.A method according to any one of claims 1 to 13, characterized in that the aluminide type coating is formed on localized areas of the surface of a metal substrate for the purpose of repairing a protective coating of the substrate. Substrat métallique muni d'un revêtement de protection comprenant un revêtement de type aluminiure incorporant au moins un élément réactif et formé à la surface du substrat, caractérisé en ce que le revêtement en aluminiure est obtenu par le procédé de l'une quelconque des revendications 1 à 14.Metal substrate provided with a protective coating comprising an aluminide type coating incorporating at least one reactive element and formed on the surface of the substrate, characterized in that the aluminide coating is obtained by the process of any one of claims 1 to 14. Substrat métallique selon la revendication 15, caractérisé en ce que le revêtement de protection comprend en outre un revêtement externe en céramique ancré sur le revêtement de type aluminiure.Metal substrate according to claim 15, characterized in that the protective coating further comprises an external ceramic coating anchored on the coating of the aluminide type. Substrat métallique selon l'une quelconque des revendications 15 et 16, caractérisé en ce que le revêtement de type aluminiure incorpore en outre au moins un métal choisi dans le groupe constitué par le platine, le palladium, le rhodium et le ruthénium.Metallic substrate according to either of Claims 15 and 16, characterized in that the aluminide-type coating additionally incorporates at least one metal chosen from the group consisting of platinum, palladium, rhodium and ruthenium. Substrat métallique en superalliage selon l'une quelconque des revendications 15 à 17, caractérisé en ce qu'il constitue une pièce de turbine à gaz.Metal superalloy substrate according to any one of Claims 15 to 17, characterized in that it constitutes a gas turbine part.
EP01402232A 2000-08-28 2001-08-27 Method of forming a reactive-element containing aluminide on a metallic substrate Ceased EP1184479A1 (en)

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FR0011000A FR2813318B1 (en) 2000-08-28 2000-08-28 FORMATION OF AN ALUMINIURE COATING INCORPORATING A REACTIVE ELEMENT, ON A METAL SUBSTRATE
FR0011000 2000-08-28

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US6673709B2 (en) 2004-01-06
FR2813318B1 (en) 2003-04-25
JP2002146555A (en) 2002-05-22
FR2813318A1 (en) 2002-03-01
RU2276699C2 (en) 2006-05-20
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CA2356305A1 (en) 2002-02-28
UA76937C2 (en) 2006-10-16

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