EP3284843A1 - Enduit au trempé stable à long terme, stockable pour revêtements de diffusion écologiques - Google Patents

Enduit au trempé stable à long terme, stockable pour revêtements de diffusion écologiques Download PDF

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Publication number
EP3284843A1
EP3284843A1 EP17186022.4A EP17186022A EP3284843A1 EP 3284843 A1 EP3284843 A1 EP 3284843A1 EP 17186022 A EP17186022 A EP 17186022A EP 3284843 A1 EP3284843 A1 EP 3284843A1
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EP
European Patent Office
Prior art keywords
long
metal
term stable
slip
alloy
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.)
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Application number
EP17186022.4A
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German (de)
English (en)
Inventor
Johannes Bauer
Jonathan BLOH
Melanie Braun
Francesco Depentori
Wolfram FÜRBETH
Mathias GALETZ
Xabier MONTERO
Michael Schütze
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DECHEMA -Forschungsinstitut
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DECHEMA -Forschungsinstitut
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Publication date
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Publication of EP3284843A1 publication Critical patent/EP3284843A1/fr
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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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/18—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions
    • C23C10/20—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions only one element being diffused
    • 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
    • C23C10/18—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions
    • C23C10/26—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions more than one element being diffused
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134—Plasma spraying

Definitions

  • the present application is concerned with the production and use of long-term stable, storable slips for environmentally friendly diffusion coatings, wherein in addition to the metals used for the diffusion coating also the corresponding metal oxides are incorporated into the slip composition and a targeted adjustment of the slip viscosities to avoid sedimentation.
  • Diffusion layers are used to protect against high temperature corrosion.
  • a metallic oxide-forming element is enriched by diffusion.
  • the most widely used diffusion metal is aluminum.
  • other metals especially Cr, Ge, Mg, Mn, Si, Sn, Ti, Zn.
  • alloys such as AlSi12 or a Cr-Al alloy with 50-80% Cr (see US 6,110,262 ) to be used for the Eindiffusion, whereby several oxide formers are present simultaneously in the edge zone. To produce such coatings, different methods can be used.
  • the pack cementing process (a CVD process), which is used eg for aircraft gas turbines.
  • the metal to be diffused is conveyed by means of an activator at high temperatures through the gas phase from a powder package surrounding the component to the component surface and separated. Subsequently, solid-state diffusion occurs, whereby relatively long heat treatments are required to produce sufficiently thick diffusion layers.
  • the element enrichment can be effected by a slip method.
  • newer slip methods are based on an exothermic reaction between the diffusion metal and the elements of the base material in combination with a Surface heat treatment.
  • the diffusion metal After reaching the melting temperature of the diffusion metal when heating the system, this wets the surface. As a result, there is an exothermic reaction between the diffusion metal and elements of the substrate (eg Al reacts with Fe or Ni) associated with a strong, local increase in temperature. This process is completed within a few seconds. Subsequently, the desired phases are adjusted by further heat treatment via solid-state diffusion. So that a proper slip coating can be achieved, the slurry must meet various requirements, which will be discussed in more detail below.
  • a slurry as a suspension consisting of one or more solids in a liquid.
  • a suspension consisting of a solvent, the metal to be diffused as powder and a binder (taken together a so-called precursor) is applied to the surface of the material to be coated.
  • a drying step and the diffusion process.
  • the composition of the slip used varies greatly and depends on the coating method chosen (eg brushing, spraying, dipping or tape casting) and the material to be coated.
  • the various components of a commercial slurry of the prior art fulfill various tasks. Above all, the solvent serves to ensure the processability for the selected application method and to take up the filler or the diffusion metal.
  • organic solvents or water are used for this purpose.
  • a binder is used.
  • organic compounds or acids eg phosphoric acid up to a proportion of 30%
  • chromium (VI) compounds are used for this purpose.
  • the binder ensures that the slip suspension does not completely separate or sediment and that it retains its processability by shaking or the like.
  • the proportions of solvent, binder and filler also set the viscosity, which is decisive for the chosen processing method.
  • a novel approach underlying the present patent provides, inter alia, for the binder to prevent the reaction of the solvent with the diffusion metal.
  • successful, water-based and environmentally friendly slurry with polyvinyl alcohol as a binder and eg Al as a diffusion metal must always be stirred in a timely manner, otherwise it comes to hydrogen evolution.
  • the naturally occurring, thin and reaction-preventing Al 2 O 3 layer on the Al powder particles is dissolved in the presence of water, and elemental aluminum reacts in sequence with the water to Al 2 O 3 and H 2 .
  • this system tends to sedimentation, and there is no simple remixability. This hampers the commercial use of this slip system and is solved by the innovative approach of this patent, so that a long-term stable slip which can be handled without endangering humans and the environment is available.
  • the invention provides that prior to mixing the slurry of the binder is modified accordingly, so that the contact between binder and metal particles no longer leads to hydrogen formation and sedimentation of the particles is prevented. This procedure is so far neither realized nor suggested in the prior art methods.
  • the present invention therefore relates to long-term stable slip as a precursor for slip-based diffusion coatings, characterized in that embedded in the slurry metallic particles at Storage show no significant reactions with the binder medium and do not sediment.
  • the long-term stable slip is characterized in that it is a water-based suspension comprising the following constituents: (i) metallic particles, in particular one or more metals or metal alloys as pulverulent particles, (ii) one or more metal oxides corresponding to the metals or metal alloys used, and (iii) a binder medium, in particular a binder medium comprising: one or more binders, one or more thixotropic agents and / or gelling agents, and, optionally, a buffer system and / or an activator for the diffusion process in the diffusion layer production.
  • the pH of the slip composition is in the range of 4 to 15.
  • the metal oxide or metal oxides are undissolved in particulate form in the slip
  • the expression "undissolved in particulate form in the slip before” means that the oxides added in particulate form to more than 90%, in particular more than 95%, more than 98%, more than 99% or more than 99.5% remain unresolved.
  • each of the oxides used is undissolved in particulate form.
  • Al, Co, Cr, Fe, Mg, Mn, Ni, Sn, Ti, Zn or their alloys will be used for the metallic particles.
  • a further embodiment is characterized in that, in addition to the metallic particles, particles of semimetals, such as e.g. B, Ge and Si, or their alloys are used.
  • one or more metals and / or semimetals are selected from the following list for the metallic particles: Al, Si, Ge, Ti, Cr, Mn, Zn, and Sn.
  • composition of the slurry depends on the expected corrosive and mechanical stresses.
  • layers produced by means of Sn or Ge-modified slip have proven to be particularly resistant to metal dusting attack, and Si and Cr modified layers are particularly suitable for hot gas corrosion.
  • Cr-modified diffusion layers have higher ductility and thus ductility at room temperature than pure aluminide layers. It is also possible to use a combination of several metal particles or their alloys for the production of slip.
  • the present invention relates to long-term stable slips, which are characterized in that an alloy is used for the metallic particles selected from: Cr-Al alloy (in the range of about 10 to about 50 wt .-% Cr) , Al-Ge alloy (in the range of about 10 to about 50 wt.% Ge), Al-B alloy (in the range of about 1 to about 20 wt.% B), Al-Ti alloy (in the range from about 25 to about 80 wt.% Ti), Al-Co alloy (in the range of about 2 to about 70 wt.% Co), Al-Si alloy (in the range of about 2 to about 20 wt. % Si), Al-Fe alloy (in the range of about 50% to about 90% by weight).
  • Fe Al-Mn alloy (in the range of about 30 to about 50 weight percent Mn), Al-Ni alloy (in the range of about 40 to about 90 weight percent Ni).
  • the term "about XX” means that the actual value of the quantity characterized thereby is within a range of 90% to 110% of the indicated value XX, especially within a range of 95% to 105%. , especially within a range of 97.5% to 102.5%, especially within a range of 99% to 101%.
  • the term "about XX” includes the exact value XX.
  • range indications such as "in the range of about XX to about YY"
  • the indication is to be understood such that the quantity characterized thereby is within a range of 90% of the specified value XX to 110% of the specified value YY, especially within one range from 95% of the declared value XX to 105% of the declared value YY, especially within a range of 97.5% of the declared value XX to 102.5% of the declared value YY, especially within a range of 99% of the declared value XX to 101% of the stated value Value YY.
  • the term "about XX to about YY" includes the exact range XX to YY.
  • the metallic particles have a content in the slurry in the range of about 20 vol.% To about 80 vol.%, In particular in the range of about 20 vol.% To about 70 vol.%.
  • the volume fraction of metal particles and binder in the slurry varies depending on particle type, mode of application and application. Small volume fractions of metal particles are e.g. used for dip coatings with 40% and less In spray coatings, the volume fraction of metal particles in the range of about 30 to about 60%. For application with a brush, the volume fraction is about 20 to about 80%.
  • the metallic particles have on average a particle size in the size range of about 1 to about 100 microns.
  • the average particle size can be determined by one of the following methods: Laser Diffraction Analysis / Spectroscopy, Scanning Electron Microscopy, Transmission Electron Microscopy.
  • the standard deviation from the mean is at most about ⁇ 15%.
  • the long-term stable slip of the present invention is characterized in that forms on the metallic particles, a passive layer in contact with the binder medium or a passive layer is present even before introduction into the binder medium.
  • metal particles are used for the slip, which have already formed a thin oxide layer with atmospheric oxygen. This happens e.g. during storage of the metal particles in air and ambient temperature for a sufficiently long period of time (1 month and more).
  • the passive layer is stabilized against dissolution by dispersing one or more metal oxides corresponding to the metal or metal alloys used in the slurry.
  • the amount of oxide to be added depends on the solubility product of the oxide and is usually very small.
  • the metal oxides are selected from the list: Al 2 O 3 for Al, B 2 O 3 for B; CoO for Co, Cr 2 O 3 for Cr, GeO 2 for Ge, MgO for Mg, MnO 2 for Mn, SiO 2 for Si, SnO 2 for Sn, TiO 2 for Ti, and ZnO for Zn, where for alloys the oxides the respective alloy components are used.
  • the metal oxide or metal oxides are present as particles having an average particle size in the size range of about 0.1 to about 10 microns.
  • the mean particle size of the metal oxides can be determined by one of the following methods: Laser Diffraction Analysis / Spectroscopy, Scanning Electron Microscopy, Transmission Electron Microscopy.
  • the standard deviation from the mean is at most about ⁇ 15%, the mean should be similar to the mean of the metal powder or smaller.
  • the metal oxides have a proportion in the slip in the range of about 0.005 vol.% To about 10 vol.%.
  • the total amount of metallic particles and metal oxides in the slurry is in the range of about 20% to about 80% by volume, more preferably in the range of about 20% to about 70% by volume.
  • the passive layer of the embedded metallic particles is stabilized against dissolution by adjusting the pH of the slurry into the passive range of the metal or of the metals of the metal particles dispersed in the slip.
  • passive range of a metal is to be understood as the pH range in which a passivating metal oxide or metal hydroxide layer is chemically stable and prevents further reactions between medium and metal.
  • the pH of the binder must be adjusted accordingly. At higher or lower pH values, the oxide layer is also dissolved, and in aqueous solution again a reaction takes place between the water and the metal surface, which leads to hydrogen formation.
  • the pH is selected from one of the ranges: between about pH 4 and about pH 10 for Al, between about pH 5 and about pH 12 for Cr, between about pH 6 and about pH 14 for Co, between about pH 4 and about pH 12 for Ge, between about pH 11 and about pH 16 for Mg, between about pH 5 and about pH 13 for Mn, between about pH 4 and about pH 12 for Si, between about pH 6 and about pH 11 for Sn, between about pH 7 and about pH 14 for Zn.
  • buffer system borate buffer H 3 BO 3 / Na 2 B 4 O 7 for the adjustment of the desired pH range, all conventional buffer systems are suitable, in particular the buffer system borate buffer H 3 BO 3 / Na 2 B 4 O 7 .
  • the metallic particles consist essentially of Al
  • the pH is selected from the range between about pH 7 and about pH 9, in particular wherein a borate buffer is used, in particular a mixture of about 0.3 MH 3 BO 3 and about 0.75 M Na 2 B 4 O 7 .
  • the term "essentially of Al” is to be understood as meaning that the particles thus characterized consist of Al and, in addition, only production-related impurities and optionally products due to reaction of the particle surface, for example by oxidation and / or hydrolysis can.
  • the particles are comprised of at least about 95% metallic aluminum, more preferably at least about 97%, at least about 98%, at least about 99%, or at least about 99.5% metallic aluminum.
  • the binder medium is free of chromate and phosphate.
  • the binder medium contains water or an aqueous mixture as binder.
  • the binder medium contains water soluble polymers such as e.g. Polyvinyl alcohol or polyethylene glycol.
  • the binder medium comprises a combination of polyvinyl alcohol as binder and water as solvent, in particular a combination of one part polyvinyl alcohol and about 10 parts of distilled water.
  • the binder medium contains a binder based on polyethylene glycol.
  • the binder medium contains one or more thixotropic agents and / or gelling agents.
  • thixotropic agent means an agent which causes a solution or suspension under the action of shear forces, such as when applying a slurry to a substrate, a relatively low viscosity, while the solution or suspension is relatively speaking without the action of shearing forces has higher viscosity. Examples of thixotropic agents in the context of the present invention are mentioned below.
  • gelling agent is to be understood as meaning an agent which leads to the formation of gel structures in a solution or suspension. Examples of gelling agents in the context of the present invention are mentioned below.
  • Sedimentation of the slurry is prevented by the addition of a thixotroping and / or gelling agent as a thickening agent.
  • a thixotroping and / or gelling agent as a thickening agent.
  • the following environmentally friendly substances are available: xanthan, pectin, nanocellulose, fumed silica. So much thickener is added until the desired viscosity and shear capacity is achieved, and the application of the slurry is still practicable.
  • the invention relates to a composition consisting essentially of at least two separate containers, these at least two separate containers containing the following components, either separately or in the form of partial mixtures: (i) metallic particles, in particular one or more metals or metal alloys as powders, (ii) one or more metal oxides corresponding to the metals or metal alloys used, (iii) one or more binders, (iv) one or more thixotropic agents and / or gelling agents, (v) a buffer system and (vi ) an activator for the diffusion process in the diffusion layer production.
  • the present invention relates to a process for the diffusion coating of a substrate, characterized in that a long-term stable slurry according to the present invention is applied to the substrate.
  • the invention relates to a method characterized in that a multi-layered green sheet for diffusion coating is produced, wherein two or more long-term stable slips according to the present invention with different viscosity are applied to the substrate.
  • the viscosities of the individual long-term stable slip are in a range from about 10 3 mPa * s to about 10 6 mPa * s.
  • the present invention relates to a process for diffusion coating a substrate, characterized in that a multi-layered green sheet for the diffusion coating is prepared, wherein two or more long-term stable slurry according to the present invention with different particle sizes and / or different particle proportions on the Substrate are applied.
  • the present invention relates to a process for the preparation of a long-term stable slip, characterized in that a suspension is prepared from the following components: (i) metallic or semi-metallic particles, in particular one or more metals or metal alloys as powder, ii) one or more metal oxides corresponding to the metal (s) used, (iii) one or more binders, (iv) one or more thixotropic agents and / or gelling agents, (v) and, optionally, a buffer system and / or an activator for the diffusion process in the diffusion layer production.
  • a suspension is prepared from the following components: (i) metallic or semi-metallic particles, in particular one or more metals or metal alloys as powder, ii) one or more metal oxides corresponding to the metal (s) used, (iii) one or more binders, (iv) one or more thixotropic agents and / or gelling agents, (v) and, optionally, a buffer system and / or an activator for the diffusion
  • composition according to the present invention is used to prepare the suspension.
  • the metallic particles are stored prior to the preparation of the suspension to form a passive layer in an oxygen-containing atmosphere and at ambient temperature or elevated temperature.
  • the metal oxide (s) corresponding to the metal or metal alloys used are added to the binder, and the metallic particles are added only when the Solubility product of the metal oxide or metal oxides in the binder, in particular in an aqueous solution.
  • the binder is admixed with the corresponding metal oxide in powder form and stored for a sufficient time until the solubility product of the metal oxide has settled in the aqueous solution.
  • This addition is intended to prevent the very thin, already present on the metal powder oxide layer is dissolved and the metal particles in the aqueous solution with the oxygen from the water and thereby release hydrogen.
  • the present invention relates to a long-term stable slip obtained by a method according to the present invention.
  • the present invention relates to a slurry-substrate complex having a substrate coated on the surface with one or more long-term stable slips according to the present invention.
  • FIG. 1 shows the experimental setup for the study of hydrogen evolution.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
EP17186022.4A 2016-08-12 2017-08-11 Enduit au trempé stable à long terme, stockable pour revêtements de diffusion écologiques Withdrawn EP3284843A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102016009854.6A DE102016009854A1 (de) 2016-08-12 2016-08-12 Langzeitstabiler, lagerfähiger Schlicker für umweltfreundliche Diffusionsbeschichtungen

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EP3284843A1 true EP3284843A1 (fr) 2018-02-21

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* Cited by examiner, † Cited by third party
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DE102022112093A1 (de) * 2022-05-13 2023-11-16 Dechema-Forschungsinstitut Verfahren zur Diffusionsbeschichtung mit einem Cr-Si-haltigen Schlicker

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69325558T2 (de) 1992-05-19 1999-10-28 Rolls-Royce Plc, London Mehrschichtiger aluminid-silicid-überzug
DE19824792A1 (de) 1998-06-03 1999-12-16 Mtu Muenchen Gmbh Verfahren zum Herstellen einer korrosions- und oxidationsbeständigen Schicht
EP0984074A1 (fr) * 1998-08-31 2000-03-08 Sermatech International Inc. Compositions de barbotine pour revêtements obtenues par diffusion
US6368394B1 (en) 1999-10-18 2002-04-09 Sermatech International, Inc. Chromate-free phosphate bonding composition
EP1671766A2 (fr) * 2004-12-17 2006-06-21 BEGO Bremer Goldschlägerei Wilh. Herbst GmbH & Co. KG Procédé de fabrication d'un creuset en céramique
US20070287013A1 (en) 2003-08-04 2007-12-13 General Electric Company Aluminizing slurry Compositions Free of Hexavalent Chromium, and Related Methods and Articles
EP2441855A2 (fr) * 2010-10-13 2012-04-18 Walbar Inc. Procédé de formation d'un revêtement d'aluminure à diffusion sur une surface d'un composant de turbine et pâte homogène pour le revêtement de telles surfaces
WO2013149609A1 (fr) 2012-04-03 2013-10-10 Mtu Aero Engines Gmbh Barbotine et procédé de production d'une couche de diffusion en aluminium
WO2015044559A1 (fr) * 2013-09-24 2015-04-02 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procédé de dépôt d'un revêtement protecteur contre la corrosion

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69325558T2 (de) 1992-05-19 1999-10-28 Rolls-Royce Plc, London Mehrschichtiger aluminid-silicid-überzug
DE19824792A1 (de) 1998-06-03 1999-12-16 Mtu Muenchen Gmbh Verfahren zum Herstellen einer korrosions- und oxidationsbeständigen Schicht
EP0984074A1 (fr) * 1998-08-31 2000-03-08 Sermatech International Inc. Compositions de barbotine pour revêtements obtenues par diffusion
US6110262A (en) 1998-08-31 2000-08-29 Sermatech International, Inc. Slurry compositions for diffusion coatings
US6368394B1 (en) 1999-10-18 2002-04-09 Sermatech International, Inc. Chromate-free phosphate bonding composition
US20070287013A1 (en) 2003-08-04 2007-12-13 General Electric Company Aluminizing slurry Compositions Free of Hexavalent Chromium, and Related Methods and Articles
EP1671766A2 (fr) * 2004-12-17 2006-06-21 BEGO Bremer Goldschlägerei Wilh. Herbst GmbH & Co. KG Procédé de fabrication d'un creuset en céramique
EP2441855A2 (fr) * 2010-10-13 2012-04-18 Walbar Inc. Procédé de formation d'un revêtement d'aluminure à diffusion sur une surface d'un composant de turbine et pâte homogène pour le revêtement de telles surfaces
WO2013149609A1 (fr) 2012-04-03 2013-10-10 Mtu Aero Engines Gmbh Barbotine et procédé de production d'une couche de diffusion en aluminium
WO2015044559A1 (fr) * 2013-09-24 2015-04-02 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procédé de dépôt d'un revêtement protecteur contre la corrosion

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