EP2956566B1 - Procede de depot d'un revetement contre la corrosion - Google Patents

Procede de depot d'un revetement contre la corrosion Download PDF

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Publication number
EP2956566B1
EP2956566B1 EP14708611.0A EP14708611A EP2956566B1 EP 2956566 B1 EP2956566 B1 EP 2956566B1 EP 14708611 A EP14708611 A EP 14708611A EP 2956566 B1 EP2956566 B1 EP 2956566B1
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EP
European Patent Office
Prior art keywords
cement
substrate
coating
recovered
spherical particles
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.)
Active
Application number
EP14708611.0A
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German (de)
English (en)
French (fr)
Other versions
EP2956566A1 (fr
Inventor
Nicolas Richet
Thierry Mazet
Michel VILASI
Stéphane MATHIEU
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Universite de Lorraine
Original Assignee
Centre National de la Recherche Scientifique CNRS
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Universite de Lorraine
Priority date (The priority date 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 date listed.)
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Publication of EP2956566A1 publication Critical patent/EP2956566A1/fr
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Publication of EP2956566B1 publication Critical patent/EP2956566B1/fr
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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
    • C23C10/36—Embedding in a powder mixture, i.e. pack cementation only one element being diffused
    • C23C10/48—Aluminising
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • 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
    • C23C10/28—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
    • C23C10/54—Diffusion of at least chromium
    • C23C10/56—Diffusion of at least chromium and at least aluminium
    • 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
    • C23C10/60—After-treatment

Definitions

  • the present invention relates to the production of a protective coating against corrosion on a substrate having cavities.
  • Thermal spraying techniques such as plasma or flame projection involves sending molten or partially melted particles, at high speed, to the surface of the part to be protected.
  • the coating is constructed in successive layers. These techniques can only be used on open or easily accessible surfaces.
  • the vapor phase deposition techniques use a gaseous precursor of the coating to be produced.
  • This precursor may be produced in the direct vicinity of the surface to be coated (carburized pack) or transported via a gas to the surface to be coated (out of pack, CVD from a bottle or gaseous mixture, etc.).
  • the main difficulties encountered for the carburizing pack are related to the filling of parts having a complex geometry or very small dimensions (a few mm) with the cementum powder (precursor mixture of the coating).
  • the main limitations of the techniques using gaseous precursors concern the rapid depletion of the gaseous mixture in reactive species resulting in heterogeneities of chemical composition and / or thickness of the coating. It is very difficult to obtain a homogeneous coating on large surfaces or in complex geometries.
  • Physical vapor deposition techniques involve evaporating the component (s) of the coating prior to condensing them on the surface of the part to be coated. Evaporation is usually done by bombarding a target with a high energy beam (electrons or ions). The distance between the target and the surface to be coated is a major parameter for the homogeneity of the thickness of the deposit. These techniques are very difficult to use on parts of complex geometry or on non-accessible surfaces.
  • the carburizing pack is a very old process for making a coating on a part.
  • the latter is placed in a bed of cementum powder, which is a mixture of products capable of generating a reactive atmosphere at high temperature.
  • This cementum should be placed close to the surface to be coated to produce a homogeneous coating in thickness and chemical composition.
  • Coatings are conventionally made on parts having cavities of a few centimeters by filling the part with the cementum powder.
  • a solution of the present invention consists in the use of a cementum in a pack-cementation deposition process on a substrate having cavities of minimum equivalent diameter e cm , characterized in that the cementum consists of spherical particles presenting each a diameter d such that d ⁇ e cm / 10.
  • the size of the cement particles can be measured by laser granulometry or sieves to ensure that no particle or agglomerate of cement particles exceeds the maximum size required.
  • a disagglomeration step may be necessary to "break" the agglomerates of elementary particles that may exceed the maximum size required.
  • the equivalent diameters of the particles are conventionally between 1 .mu.m to 1 mm, preferably between 1 .mu.m and 100 .mu.m.
  • the equivalent diameter is defined as the diameter of the cylinder or circle that fits into the smallest section giving access to the surface to be coated. Indeed, the latter does not necessarily have a standard form.
  • the inert compound does not chemically intervene in the formation of the coating. Its main function is to avoid the densification of the cementum which would prevent its elimination after deposit. It is usually a very stable refractory compound. Its content is the complement of the other two.
  • the solution according to the invention allows the realization of a deposit by pack cementation on parts of complex geometry and in inaccessible cavities.
  • the cementum used in the context of the invention has a very good flowability to fill the smallest gaps (diameter ⁇ 1mm) and distribute evenly within the entire cavity to be coated.
  • the particle size distribution and the morphology of the cement particles are the main parameters to ensure a good flowability of the mixture.
  • the particle size distribution is adjusted according to the equivalent diameter of the smallest passage of the cavity.
  • morphology spherical shapes which can be obtained by different grinding techniques for powders or powder mixture.
  • An atomization treatment of the powder mixture may also be used to form spheres of the powder mixture.
  • organic additives may be used to ensure a good cohesion of the spheres and a homogeneous dispersion of the elements of the mixture.
  • the present invention also relates to two methods of depositing a coating by pack cementation on a substrate having cavities of minimum equivalent diameter e cm .
  • step c) the substrate-cement element is heated at about 650 ° C. for at least 6 hours.
  • the figure 1 schematizes the different steps of the first method according to the invention.
  • the first process consists in the use of a powder mixture consisting of the activating agent (5%), an inert diluent (Alumina, silica, etc.) and a metal to be deposited, a metal powder ( between 10 and 60%) which can be either pure aluminum or an Al + NiAl or AlCr mixture and whose particles may or may not have been "pre-activated" by mechano-synthesis.
  • the granulometry of the mixture is then adjusted so that it can be introduced into the channels by a vibratory system.
  • the assembly is then brought to a temperature below the melting temperature of the metal to be deposited for a period of at least 6 hours.
  • the assembly is again subjected to a vibration step for extracting the residual powder.
  • the coating consists of a surface enrichment of aluminum substrate whose composition is close to NiAl 3 .
  • the thicknesses obtained vary between 5 and 10 microns depending on the time during which the first heating step was carried out.
  • the part thus coated is brought to a temperature of between 900 ° C. and 1150 ° C., preferably greater than 980 ° C., so as to obtain the NiAl composition in a superficial edge of thickness ranging from 15 to 25 ⁇ m ( figure 3 ).
  • the figure 2 schematizes the different steps of the second method according to the invention.
  • the second method consists in the use of a pulverulent mixture consisting of a low melting point stripping flux (K 3 AlF 6 -KAlF 4 ) which is the element which has the lowest melting point of cement mixture and particles of an inert diluent and a pure metal powder or aluminum alloy. (10 to 60% of metal powders, 40% of stripping flux and the balance of inert diluent).
  • K 3 AlF 6 -KAlF 4 low melting point stripping flux
  • the whole is introduced by vibration as in the case of the first method and is heated to a high temperature, lower than the melting of the metal phase, but greater than that of the stripping flux for a time that varies from a few minutes to one or two hours. .
  • the coating is obtained either under primary vacuum or inert controlled atmosphere (argon).
  • the residues are then extracted by washing directly after the heat treatment step.
  • the apparatus can be washed with a chemical solution (acidified aqueous).
  • the coating thus obtained corresponds to a phase of composition close to NiAl 3 which can be converted into NiAl in a subsequent annealing step at a temperature between 900 ° C and 1150 ° C, preferably at 980 ° C.
  • the appearance of the coating is shown in FIG.
  • the powder mixtures can be stored for long periods of time in a desiccator under a primary vacuum or in a dry chamber under a neutral gas sweep and are immediately ready for use.
  • the inert diluent is chosen from powders of refractory inert materials, more preferably from refractory mineral oxides, such as alumina, silica, magnesia and mixtures thereof, which are commonly used in cementation.
  • refractory inert materials more preferably from refractory mineral oxides, such as alumina, silica, magnesia and mixtures thereof, which are commonly used in cementation.
  • the substrate which can be provided with such a coating is generally chosen from metal substrates, for example iron or nickel base, alloy (s) substrates or superalloy (s), composite substrates comprising one or more metals and / or alloy (s) and / or superalloy (s) containing Ni to react with the deposited Al and form NiAl.
  • metal substrates for example iron or nickel base, alloy (s) substrates or superalloy (s), composite substrates comprising one or more metals and / or alloy (s) and / or superalloy (s) containing Ni to react with the deposited Al and form NiAl.
  • the substrate may be previously superficially enriched in Ni for example by electrolytic deposition.
  • the treatments are generally carried out under a neutral or reducing atmosphere, for example under an atmosphere of hydrogen and / or argon, preferably under an argon atmosphere, or under an argon atmosphere with, for example, from 5 to 10% of argon. hydrogen.
  • the pressure used during the treatment may be atmospheric pressure or a reduced pressure, for example a pressure of 10 -2 atm of argon.
  • the coatings obtained by the processes according to the invention give the substrates an excellent resistance to corrosion, even within each substrate cavity regardless of its size.
  • the photos of the figure 3 show two samples of HR120 alloy, one (the one on the right) coated with the coating developed according to the second method according to the invention and the other (the left one) uncoated. These samples were subjected to a corrosive atmosphere consisting of (in% vol.): 15% CO, 5% CO 2 , 55% H 2 , 25% H 2 O, at a pressure of 21 bar absolute and a temperature of 650 ° C. After 4700 hours of exposure, it is clear that the coating deposited according to the second method of the invention protects the alloy from corrosion.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Powder Metallurgy (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Chemically Coating (AREA)
EP14708611.0A 2013-02-13 2014-02-04 Procede de depot d'un revetement contre la corrosion Active EP2956566B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1351227A FR3001976B1 (fr) 2013-02-13 2013-02-13 Procede de depot d'un revetement contre la corrosion
PCT/FR2014/050193 WO2014125187A1 (fr) 2013-02-13 2014-02-04 Procede de depot d'un revetement contre la corrosion

Publications (2)

Publication Number Publication Date
EP2956566A1 EP2956566A1 (fr) 2015-12-23
EP2956566B1 true EP2956566B1 (fr) 2016-11-23

Family

ID=48570257

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14708611.0A Active EP2956566B1 (fr) 2013-02-13 2014-02-04 Procede de depot d'un revetement contre la corrosion

Country Status (7)

Country Link
US (1) US20150368782A1 (zh)
EP (1) EP2956566B1 (zh)
JP (1) JP2016510089A (zh)
CN (1) CN105164303B (zh)
FR (1) FR3001976B1 (zh)
WO (1) WO2014125187A1 (zh)
ZA (1) ZA201505484B (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3062324B1 (fr) * 2017-01-30 2019-03-22 Safran Aircraft Engines Procede de fabrication de pieces realisees en metallurgie des poudres comportant l’application d'un revetement
FR3133769A1 (fr) 2022-03-23 2023-09-29 Fives Cryo Procede de revetement de surfaces internes d’un echangeur par un solide pulverulent

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1379731A (en) * 1971-01-05 1975-01-08 Albright & Wilson Chromising ferrous metal substrates
NL7410717A (nl) * 1973-08-13 1975-02-17 Albright & Wilson Gewoon staal met laag koolstofgehalte.
US4156042A (en) * 1975-04-04 1979-05-22 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Coating articles having fine bores or narrow cavities in a pack-cementation process
JPH07113146B2 (ja) * 1985-01-23 1995-12-06 株式会社日立製作所 アルミニウムまたはその合金の表面処理方法
JPS62212100A (ja) * 1986-03-14 1987-09-18 Canon Inc 粉末充填方法及び該方法に使用する装置
DE4035790C1 (zh) * 1990-11-10 1991-05-08 Mtu Muenchen Gmbh
EP0496935B1 (en) * 1991-01-31 1995-04-19 General Electric Company Aluminide processing of articles protected by a thermal barrier coating system
US5441767A (en) * 1994-01-26 1995-08-15 United Technologies Corporation Pack coating process for articles containing small passageways
JPH10298779A (ja) * 1997-04-25 1998-11-10 Hitachi Ltd ガスタービンバケットの製造方法
DE19856901C2 (de) * 1998-12-10 2003-01-16 Mtu Aero Engines Gmbh Verfahren zum Beschichten von Hohlkörpern
US6299935B1 (en) * 1999-10-04 2001-10-09 General Electric Company Method for forming a coating by use of an activated foam technique
JP2001254163A (ja) * 2000-12-18 2001-09-18 Ichiro Kawakatsu ＮｉまたはＮｉ合金基体に対するＡｌまたはＡｌ合金の被覆法
US7094445B2 (en) * 2002-05-07 2006-08-22 General Electric Company Dimensionally controlled pack aluminiding of internal surfaces of a hollow article
GB0409486D0 (en) * 2004-04-28 2004-06-02 Diffusion Alloys Ltd Coatings for turbine blades
US7252480B2 (en) * 2004-12-17 2007-08-07 General Electric Company Methods for generation of dual thickness internal pack coatings and objects produced thereby
JP5403881B2 (ja) * 2007-07-10 2014-01-29 ゼネラル・エレクトリック・カンパニイ ジェットエンジンブレードのサーペンタイン冷却通路のアルミナイジング法
FR2921937B1 (fr) * 2007-10-03 2009-12-04 Snecma Procede d'aluminisation en phase vapeur d'une piece metallique de turbomachine
US8501273B2 (en) * 2008-10-02 2013-08-06 Rolls-Royce Corporation Mixture and technique for coating an internal surface of an article
JP2010112671A (ja) * 2008-11-10 2010-05-20 Showa Denko Kk 熱交換器用チューブの製造方法

Also Published As

Publication number Publication date
FR3001976A1 (fr) 2014-08-15
US20150368782A1 (en) 2015-12-24
ZA201505484B (en) 2016-04-28
EP2956566A1 (fr) 2015-12-23
JP2016510089A (ja) 2016-04-04
CN105164303A (zh) 2015-12-16
CN105164303B (zh) 2018-04-20
FR3001976B1 (fr) 2015-02-20
WO2014125187A1 (fr) 2014-08-21

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