US20150368782A1 - Method for depositing a corrosion-protection coating - Google Patents
Method for depositing a corrosion-protection coating Download PDFInfo
- Publication number
- US20150368782A1 US20150368782A1 US14/767,795 US201414767795A US2015368782A1 US 20150368782 A1 US20150368782 A1 US 20150368782A1 US 201414767795 A US201414767795 A US 201414767795A US 2015368782 A1 US2015368782 A1 US 2015368782A1
- Authority
- US
- United States
- Prior art keywords
- cement
- substrate
- spherical particles
- comprised
- coating
- 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.)
- Abandoned
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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 corrosion-protection coating on a substrate that has cavities.
- Thermal spraying techniques such as plasma or flame spraying consist in sending molten or partially molten particles, at high velocity, to the surface of the part to be protected.
- the coating is constructed of successive layers. These techniques can only be used on open or readily accessible surfaces.
- the vapor deposition techniques use a gaseous precursor of the coating to be produced.
- This precursor may be produced in direct proximity to the surface to be coated (pack cementation) or be transported via a gas to the surface to be coated (out of pack, CVD using a gas cylinder or mixture, . . . ).
- the main difficulties encountered for pack cementation are linked to the filling of parts that have a complex geometry or very small dimensions (several mm) with the cement powder (precursor mixture of the coating).
- the main limitations of techniques that use gaseous precursors relate to the rapid depletion of reactive species from the gaseous mixture leading to heterogeneities of chemical composition and/or of thickness of the coating. It is very difficult to obtain a uniform coating on large surfaces or in complex geometries.
- the physical vapor deposition techniques consist in evaporating the constituent element(s) of the coating before condensing them on the surface of the part to be coated.
- the evaporation generally takes place by bombarding a target with a high-energy (electron or ion) beam.
- the distance between the target and the surface to be coated is a major parameter for the uniformity of the thickness of the deposition.
- Pack cementation is a very old process for producing a coating on a part.
- the latter is placed in a bed of cement powder, which is a mixture of products capable of generating a reactive atmosphere at high temperature.
- This cement must be placed in the vicinity of the surface to be coated in order to produce a coating that is uniform in terms of thickness and chemical composition.
- Coatings are conventionally produced on parts having cavities of several centimeters by filling the part with the cement powder.
- one problem that is faced is to improve the pack cementation deposition processes in order to enable the use thereof for coating a substrate that has cavities.
- One solution of the present invention consists of the use of a cement in a process for pack cementation deposition on a substrate having cavities of minimum equivalent diameter e cm , characterized in that the cement consists of spherical particles each having a diameter d such that d ⁇ e cm /10.
- the size of the cement particles may be measured by laser particle size analysis or with the aid of a screen in order to ensure that no cement particle or agglomerate of cement particles exceeds the required maximum size.
- a step of deagglomeration may be necessary in order to “break” the agglomerates of individual particles that may exceed the required maximum size.
- the equivalent diameters of the particles are conventionally between 1 ⁇ m and 1 mm, preferably between 1 ⁇ m and 100 ⁇ m.
- the equivalent diameter is defined as the diameter of the cylinder or of the circle that is inscribed within the smallest cross section giving access to the surface to be coated. Specifically, the latter does not necessarily have a standard shape.
- the use according to the invention may have one or more of the following features:
- the cement consists of spherical particles each having a diameter d such that d ⁇ e cm /10;
- the cement comprises a precursor of the element to be deposited, an activating agent and an inert diluent
- the cement comprises 10% to 60% of metallic powder as precursor of the element to be deposited, 5% to 40% of activating agent, and a balance to 100% of inert diluent, the inert diluent preferably comprising refractory oxides;
- the metallic powder consists of aluminum or a mixture of aluminum with Ni x Al y or Al x ,Cr y , particles;
- the cement comprises a precursor of the element to be deposited, a pickling flux and an inert diluent
- the cement comprises an organic or inorganic binder.
- the organic binder may be PVA (polyvinyl acetate) and the inorganic binder may be SiO 2 .
- the organic or inorganic binder may be used during a step of atomization of the powder mixture. This optional step makes it possible to improve the flowability of the powder and therefore the filling of the part. It is a matter of forming spherical agglomerates of the powder mixture. This step will preferably be carried out under an inert atmosphere in order to avoid surface oxidation of the metallic powders which may be detrimental to the deposition.
- the inert compound is not chemically involved in the formation of the coating. Its main role is to avoid the densification of the cement which would prevent the elimination thereof after deposition. In general, it is a highly stable refractory compound. The content thereof is the balance of the other two compounds.
- the solution according to the invention enables the production of a pack cementation deposition on parts of complex geometry and in cavities that are difficult to access.
- the cement used within the context of the invention has a very good flowability that makes it possible to fill the smallest interstices (of diameter ⁇ 1 mm) and to be uniformly distributed inside the whole of the cavity to be coated.
- the particle size distribution and the morphology of the cement particles are the principal parameters for ensuring a good flowability of the mixture.
- the particle size distribution is adjusted as a function of the equivalent diameter of the smallest passage of the cavity.
- the spherical shapes which may be obtained by various techniques of grinding the powders or the powder mixture are also favored.
- An atomization treatment of the powder mixture could also be used to form spheres of the powder mixture.
- organic additives could be used to ensure a good cohesion of the spheres and a uniform dispersion of the elements of the mixture.
- the present invention also relates to two processes for depositing a coating by pack cementation on a substrate having cavities of minimum equivalent diameter e cm .
- the first process for depositing a coating by pack cementation on a substrate having cavities of minimum equivalent diameter e cm comprises the following successive steps:
- a cement consisting of spherical particles of an activating agent, of an inert diluent and of a metallic powder is prepared, said spherical particles each having a diameter d such that d ⁇ e cm /10;
- step b) the cement prepared in step a) is introduced into the cavities of the substrate by a vibrating system;
- the substrate-cement assembly is heated at a temperature below the melting point of the metallic powder for a duration of at least 6 h at around 650° C. for aluminum;
- the substrate-cement assembly is heated at a temperature of between 900° C. and 1150° C., preferably above 980° C.;
- step c) the substrate-cement assembly is heated at around 650° C. for at least 6 h.
- the first process may have one or more of the following features:
- the particles of the cement prepared in step a) are preactivated by mechanosynthesis; the preactivation makes it possible to increase the chemical reactivity of the precursor particles. This treatment facilitates the reaction between the precursor and the activator, and therefore the deposition;
- the coating recovered in step g) comprises NiAl
- the coating recovered in step g) has a thickness of between 15 and 25 ⁇ m.
- the second process for depositing a coating by pack cementation on a substrate having cavities of minimum equivalent diameter e cm comprises the following successive steps:
- a cement consisting of a pickling flux and spherical particles of an inert diluent and of a metallic powder is prepared, said spherical particles each having a diameter d such that d ⁇ e cm /10;
- step b) the cement prepared in step a) is introduced into the cavities of the substrate by a vibrating system;
- the substrate-cement assembly is heated at a temperature above the melting point of the pickling flux, under low vacuum or under an inert atmosphere (Ar), for a duration of between 10 min and 2 h;
- the cement is subjected to a washing step so as to eliminate the cement residue
- the second process may have one or more of the following features:
- the washing step e) is carried out using an acidified aqueous solution
- the coating recovered in step f) comprises NiAl 3 ;
- said process comprises, before step e), a step of heating the substrate-cement assembly at a temperature of between 900° C. and 1150° C., preferably above 980° C.;
- the coating recovered in step f) comprises NiAl
- the coating recovered in step f) has a thickness of between 5 ⁇ m and 200 ⁇ m, preferably between 5 ⁇ m and 80 ⁇ m.
- FIG. 1 schematically shows the various steps of the first process according to the invention.
- the first process consists of the use of a pulverulent mixture consisting of the activating agent (5%), of an inert diluent (alumina, silica, etc.) and of a metal to be deposited, a metallic powder (between 10% and 60%) which may be either pure aluminum or an Al+NiAl or AlCr mixture and the particles of which may or may not have been “preactivated” by mechanosynthesis.
- a pulverulent mixture consisting of the activating agent (5%), of an inert diluent (alumina, silica, etc.) and of a metal to be deposited, a metallic powder (between 10% and 60%) which may be either pure aluminum or an Al+NiAl or AlCr mixture and the particles of which may or may not have been “preactivated” by mechanosynthesis.
- the particle size of the mixture is then adjusted so that it can be introduced into the channels by a vibrating system.
- the assembly is then brought to a temperature below the melting point of the metal to be deposited for a duration of at least 6 h.
- the assembly is again subjected to a vibration step that enables the extraction of the residual powder.
- the coating consists of a surface enrichment in aluminum of the substrate, the composition of which is close to NiAl 3 .
- the thicknesses obtained vary between 5 and 10 ⁇ m depending on the time for 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 above 980° C. so as to obtain the composition NiAl in a surface border having a thickness ranging from 15 to 25 ⁇ m ( FIG. 3 ).
- FIG. 2 schematically shows the various steps of the second process according to the invention.
- the second process consists of the use of a pulverulent mixture consisting of a low melting point pickling flux (K 3 AlF 6 -KAlF 4 ), this is the element that has the lowest melting point of the mixture constituting the cement and particles, of an inert diluent and of a pure or aluminum alloy metallic powder (10% to 60% of metallic powders, 40% of pickling flux and the balance of inert diluent).
- a low melting point pickling flux K 3 AlF 6 -KAlF 4
- the coating is obtained either under low vacuum or under a controlled inert (argon) atmosphere.
- the residues are then extracted by washing directly after the heat treatment step.
- the apparatus may be washed with a chemical (acidified aqueous) solution.
- the coating thus obtained corresponds to a phase having a composition close to NiAl 3 which may be converted into NiAl during a subsequent annealing step at a temperature of between 900° C. and 1150° C., preferably at 980° C.
- the appearance of the coating is shown in FIG. 4 .
- the mixtures of powders may be stored over long durations in a desiccator under low vacuum or even in a dry chamber under inert gas flushing and are immediately ready to use.
- the inert diluent is selected 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 pack cementation treatments.
- refractory inert materials more preferably from refractory mineral oxides, such as alumina, silica, magnesia and mixtures thereof, which are commonly used in pack cementation treatments.
- the substrate which may be provided with such a coating is generally selected from metallic substrates, for example based on iron or nickel, substrates made of alloy(s) or made of superalloy(s), composite substrates comprising one or more metals and/or alloy(s) and/or superalloy(s) containing Ni in order to react with the Al deposited and form NiAl.
- the substrate could be surface-enriched with Ni beforehand, for example by electrolytic deposition.
- the treatments are generally carried out under an inert or reducing atmosphere, for example under a hydrogen and/or argon atmosphere, preferably under an argon atmosphere, or else under an argon atmosphere with for example 5% to 10% of 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 excellent resistance to corrosion, even within each substrate cavity independently of its size.
- the photos from FIG. 3 show two samples of HR120 alloy, one (the one on the right) coated with the coating produced according to the second process according to the invention and the other (the one on the left) being 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 clearly appears that the coating deposited according to the second process of the invention makes it possible to protect 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)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1351227 | 2013-02-13 | ||
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 (1)
Publication Number | Publication Date |
---|---|
US20150368782A1 true US20150368782A1 (en) | 2015-12-24 |
Family
ID=48570257
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/767,795 Abandoned US20150368782A1 (en) | 2013-02-13 | 2014-02-04 | Method for depositing a corrosion-protection coating |
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)
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 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5215785A (en) * | 1990-11-10 | 1993-06-01 | Mtu Motoren- Und Turbinen- Union Muenchen Gmbh | Method for the powder pack coating of hollow bodies |
US20100086680A1 (en) * | 2008-10-02 | 2010-04-08 | Rolls-Royce Corp. | Mixture and technique for coating an internal surface of an article |
Family Cites Families (17)
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 |
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 |
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 |
-
2013
- 2013-02-13 FR FR1351227A patent/FR3001976B1/fr not_active Expired - Fee Related
-
2014
- 2014-02-04 WO PCT/FR2014/050193 patent/WO2014125187A1/fr active Application Filing
- 2014-02-04 US US14/767,795 patent/US20150368782A1/en not_active Abandoned
- 2014-02-04 JP JP2015557491A patent/JP2016510089A/ja active Pending
- 2014-02-04 CN CN201480008464.5A patent/CN105164303B/zh not_active Expired - Fee Related
- 2014-02-04 EP EP14708611.0A patent/EP2956566B1/fr active Active
-
2015
- 2015-07-30 ZA ZA2015/05484A patent/ZA201505484B/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5215785A (en) * | 1990-11-10 | 1993-06-01 | Mtu Motoren- Und Turbinen- Union Muenchen Gmbh | Method for the powder pack coating of hollow bodies |
US20100086680A1 (en) * | 2008-10-02 | 2010-04-08 | Rolls-Royce Corp. | Mixture and technique for coating an internal surface of an article |
Non-Patent Citations (1)
Title |
---|
Tsipas et al. Boroaluminide coatings on ferriticâmartensitic steel deposited by low-temperature pack cementation, Surface & Coatings Technology 202 (2008) pp 3263-3271. * |
Also Published As
Publication number | Publication date |
---|---|
FR3001976A1 (fr) | 2014-08-15 |
EP2956566B1 (fr) | 2016-11-23 |
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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STCB | Information on status: application discontinuation |
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