EP3247516B1 - Procédé de pulvérisation à froid mettant en oeuvre une poudre métallique traitée - Google Patents

Procédé de pulvérisation à froid mettant en oeuvre une poudre métallique traitée Download PDF

Info

Publication number
EP3247516B1
EP3247516B1 EP16740623.0A EP16740623A EP3247516B1 EP 3247516 B1 EP3247516 B1 EP 3247516B1 EP 16740623 A EP16740623 A EP 16740623A EP 3247516 B1 EP3247516 B1 EP 3247516B1
Authority
EP
European Patent Office
Prior art keywords
gas
nitrogen
metal powder
minute
fluidized bed
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
EP16740623.0A
Other languages
German (de)
English (en)
Other versions
EP3247516A1 (fr
EP3247516A4 (fr
Inventor
Randolph Carlton MCGEE
Zissis A. Dardas
Ying She
Aaron T. Nardi
Michael A. KLECKA
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.)
Sikorsky Aircraft Corp
Original Assignee
Sikorsky Aircraft Corp
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.)
Filing date
Publication date
Application filed by Sikorsky Aircraft Corp filed Critical Sikorsky Aircraft Corp
Publication of EP3247516A1 publication Critical patent/EP3247516A1/fr
Publication of EP3247516A4 publication Critical patent/EP3247516A4/fr
Application granted granted Critical
Publication of EP3247516B1 publication Critical patent/EP3247516B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/145—Chemical treatment, e.g. passivation or decarburisation
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/24—Nitriding
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/80—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/16—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on nitrides

Definitions

  • Thermal spray technologies such as the cold spray process can be used for various applications such as applying metal layers to non-metallic substrates to make metal layer-containing composite articles, applying metal outer layers to substrates of a different material, for example to obtain corrosion benefits of the outer layer metal with the processability of the substrate metal, field repair of metal components, and various other additive manufacturing technology applications.
  • Titanium and titanium alloys are widely used for various applications such as aircraft, motor vehicles, and countless other applications, where they provide beneficial properties including but not limited to strength, strength:weight ratio, corrosion resistance, high specific heat, and tolerance of extreme temperatures.
  • the use of titanium alloys as metal powder used in the cold spray process has been limited by factors such as degradation of the nozzles used in the cold gas spray process and a tendency of the titanium alloys to clog nozzles used in the cold spray process.
  • Conventional approaches for dealing with such nozzle problems typically involve the use of exotic (and expensive) materials such as quartz for the cold spray nozzles, or modification of cold spray process parameters to lower temperatures or other process modifications that can cause adverse impacts to the properties of cold spray-applied material.
  • WO 2011/132874 A2 discloses a method of nitriding a surface of aluminum or aluminum alloy by cold spraying, whereby a surface of aluminum or aluminum alloy is coated by cold spraying, and then a heat treatment is performed thereon at low temperature for a short time period. Its method is suitable for nitriding a surface of Al and Al alloy, which is very difficult to be nitrided, at low production costs.
  • Its method includes removing a foreign material from a surface of a mother substrate comprising Al or Al alloy; cold spraying 15 to 50 wt% of a catalyst powder and 50 to 85 wt% of a coating agent powder on the surface of the mother substrate to form a coating layer; and heat treating the coating layer at a temperature of 450 to 630°C in a nitrogen atmosphere for 2 to 24 hours.
  • US 7,232,556 discloses nanoparticles comprising titanium, such as nanoscale doped titanium metal compounds, inorganic titanium compounds, and organic titanium compounds, their methods of manufacture, and methods of preparation of products from nanoparticles comprising titanium.
  • US 5,149,514 discloses a low temperature process for forming a coating or powder comprising one or more metals or metal compounds by first reacting one or more metal reactants with a halide-containing reactant to form one or more reactive intermediates capable of reacting, disproportionating, or decomposing to form a coating or powder comprising the one or more metal reactants.
  • a third reactant may be injected into a second reaction zone in the reactor to contact the one or more reactive intermediates formed in the first reaction zone to thereby form one or more metal compounds such as metal nitrides, carbides, oxides, borides, or mixtures of same.
  • US 5,320,686 discloses objects of titanium or titanium alloys having the surface converted to a hard and wear-resistant nitride layer with good adhesion, distributed uniformly and providing internal capillaries.
  • the objects are produced by being treated in a vacuum furnace with an atmosphere of pure nitrogen gas at a temperature of 650-1000° C and at a pressure below atmospheric pressure.
  • the thickness of the nitride layer can be controlled by controlling the treatment time and temperature.
  • a method of applying a metal comprising titanium to a substrate comprises nitriding the surface of metal powder particles comprising titanium by contacting the particles with a first gas comprising nitrogen in a fluidized bed reactor, and depositing the nitrided metal powder particles onto the substrate with cold spray deposition using a second gas.
  • the metal powder particles comprise titanium or titanium alloys Ti-6Al-4V, Ti-3Al-2.5V, Ti-5Al-2.5Sn, Ti-8Al-1Mo-1V, Ti-6Al-2Sn-4Zr-2Mo, ⁇ + ⁇ Ti-6Al-4V, or near ⁇ Ti-10V-2Fe-3Al.
  • the metal powder particles comprises titanium or titanium alloy grades 5 (Ti-6Al-4V) or 23(Ti-6Al-4V) according to ASTM B861-10.
  • the metal powder particles after nitriding comprise elemental nitrogen at the particle surface and also comprise an internal particle portion that is free of elemental nitrogen.
  • the metal powder particles after nitriding have a surface nitrogen content ranging from 5.96 wt.% to 12.22 wt.% as determined by x-ray photoelectron spectroscopy.
  • the metal powder particles after nitriding have a nitrogen:oxygen surface wt.% ratio of from 5.96:26.20 to 12.22:16.75 as determined by x-ray photoelectron spectroscopy.
  • the first gas comprises at least 1 vol.% nitrogen.
  • the first gas consists essentially of nitrogen.
  • the fluidized bed reactor is operated at a temperature of 500°C to 850°C.
  • the first gas is at a pressure of 0.11 to 0.12 MPa.
  • the space velocity of the first gas in the fluidized bed reactor is from 1 min -1 to 30 min -1 .
  • the metal powder particles are contacted with the first gas in the fluidized bed reactor for at least 1 minute.
  • the second gas comprises helium or argon.
  • the second gas comprises helium or argon and nitrogen.
  • the second gas consists essentially of helium or argon.
  • the second gas is at a temperature of 20°C to 850°C.
  • FIG. 1 An exemplary fluidized bed reactor assembly for nitriding titanium alloys is depicted in FIG. 1 .
  • the assembly includes a fluidized bed reactor 12 having inlet openings 14 disposed at one end of the reactor 12 and an outlet opening 16 disposed at the opposite end of the reactor 12.
  • the fluidized bed reactor 12 is disposed inside of an outer tubing 18, with outlet 16 extending to the outside of outer tubing 18.
  • the fluidized bed assembly is disposed in a furnace (not shown) to provide heat.
  • Thermocouples 17 and 19 are disposed to monitor temperature in the reactor 12 and outer tubing 18, respectively.
  • An inlet 20 is connected to a gas feed line 22.
  • a gas source 24 such as a storage tank or a gas-generating reactor is connected to gas feed line 22 to supply a gas feed to the fluidized bed reactor 12.
  • Other components such as mass flow controller 26, pressure regulating valve 28, pressure sensor 30, and shut-off valves 32 and 34 are also disposed in the gas feed line 22 for monitoring and controlling the flow rate and pressure of the gas delivered to the reactor 12.
  • Reactor outlet 16 is connected to outlet line 36, which is connected to a water or other liquid bubbler 38.
  • a bleed line 40 with shut-off valve 42 also connects feed line 22 to the bubbler 38, which is vented to atmosphere through exhaust port 44.
  • a gas comprising nitrogen from gas source 24 is fed through feed line 22, with the flow rate and gas pressure controlled by mass flow controller 26 and pressure regulating valve 28.
  • the nitrogen-containing gas enters the outer tubing 18 through inlet 20.
  • the gas is heated as it passes through the space between fluidized bed 12 and outer tubing 18 to enter the fluidized bed reactor 12 through inlet 14.
  • the fluidized bed reactor 12 has metal particles 46 comprising titanium disposed therein, and the upward gas flow rate through the reactor applies sufficient upward force to the particles 46 to counteract the force of gravity acting on the particles so that they are suspended in a fluid configuration in the reactor space.
  • outlet 16 can also be fitted with a filter or screen to further assist in keeping metal powder particles 46 from exiting the reactor 12.
  • Nitrogen-containing gas exits the reactor 12 through outlet 16 and flows via outlet line 36 to the bubbler 38, from which it is exhausted to the atmosphere through exhaust port 44.
  • the invention can utilize any titanium metal or titanium metal alloy, including any of the grades of titanium alloys specified in ASTM B861-10.
  • the titanium alloy comprises from 0 to 10 wt.% aluminum and from 0 to 10 wt.% vanadium.
  • the titanium alloy is an alpha-beta titanium alloy such as Ti-6Al-4V (e.g., grades 5 or 23 according to ASTM B861-10), Ti-Al-Sn, Ti-Al-V-Sn, Ti-Al-Mo, Ti-Al-Nb, Ti-V-Fe-Al, Ti-8Al-1Mo-1V, Ti-6Al-2Sn-4Zr-2Mo, ⁇ + ⁇ Ti-6Al-4V or near ⁇ Ti-10V-2Fe-3Al.
  • the titanium alloy is a Ti-6Al-4V alloy such as grade 5 or grade 23 according to ASTM B861-10.
  • the nitrogen-containing gas can contain from 1 vol.% to 100 vol.% nitrogen, more specifically from 5 vol.% to 100 vol.% nitrogen, and more specifically from 25 vol.% to 75 vol.% nitrogen. In some embodiments, the nitrogen-containing gas consists essentially of nitrogen, and in some embodiments the nitrogen-containing gas is pure.
  • the nitriding reaction conducted in the fluidized bed reactor is typically conducted at elevated temperature, compared to ambient conditions.
  • the reaction temperature in the reactor can range from 500°C to 800°C, more specifically from 600°C to 750°C, and even more specifically from 600°C to 700°C.
  • Pressures in the reactor can range from from 0.11 MPa to 0.12 MPa, and more specifically from 0.11 MPa to 0.115 MPa.
  • the flow rate of nitrogen to the reactor can vary based on factors such as reactor dimension, with exemplary flow rates of 0.0069 m/min to 0.013 m/min, more specifically from 0.0097 m/min to 0.011 m/min, and even more specifically from 0.010 m/ min to 0.0105 m/min.
  • the metal powder particles can be nitrided for periods (i.e., contact time with the nitrogen-containing gas) of at least 1 minute, for example, time periods ranging from 1 minute to 30 minutes, more specifically from 1 minute to 10 minutes, and even more specifically from 1 minute to 5 minutes.
  • the reactor In batch mode, such as depicted in the reaction scheme shown in FIG. 1 , the reactor is operated for the specified amount of time to achieve the desired contact time.
  • throughput of the particles through the reactor can be adjusted to achieve an average residence time equal to the desired contact time.
  • the particles After processing the titanium-containing metal particles in the nitrogen-containing fluidized bed reactor, the particles can have a surface nitrogen content ranging from 5.96 wt.% to 12.22 wt.%, more specifically from 5.96 wt.% to 7.90 wt.%, or from 7.90 wt.% to 9.77 wt.%, or from 9.77 wt.% to 12.22 wt.%, as determined by x-ray photoelectron spectroscopy.
  • x-ray photoelectron spectroscopy and the values specified herein are according to the protocols of according to ASTM E2735-14, Standard Guide for Selection of Calibrations Needed for X-ray Photoelectron Spectroscopy (XPS) Experiments, ASTM International, West Conshohocken, PA, 2014.
  • XPS X-ray Photoelectron Spectroscopy
  • the metal powder particles after nitriding the metal powder particles can have a nitrogen:oxygen surface wt.% ratio of from 5.96:26.20 to 7.90:21.83 as determined by x-ray photoelectron spectroscopy, and more specifically can have a nitrogen:oxygen surface wt.% ratio of from 9.77:19.99 to 12.22:16.75.
  • the use of pure titanium nitride as a cold spray applied metal can result in undesirable porosity levels in the applied material.
  • the nitriding reaction is conducted under conditions (e.g., contact time, temperature, space velocity) so that nitriding occurs on the surface of the metal particles but not throughout the interior of the particles, resulting in particles with a surface layer comprising nitrogen and at least a portion of the particles' interior being free of nitrogen.
  • conditions e.g., contact time, temperature, space velocity
  • the nitride titanium or titanium alloy metal powder is applied to a substrate with a cold spray deposition process.
  • a cold spray process unmelted metal particles are introduced into a high velocity gas stream being projected out of a high velocity (e.g., supersonic) nozzle toward the coating substrate target.
  • the particles' kinetic energy provides sufficient heat on impact with the coating substrate such that the particles plastically deform and fuse with the substrate and surrounding deposited metal material.
  • the particles impact the substrate they rapidly cool even as the particles are deforming. The particles change shape dramatically from relatively round to very thin flat splats on the surface.
  • FIG. 2 An exemplary system is depicted in FIG. 2 .
  • metal powder is fed from powder feeder 48 through conduit 49 to spray gun 50, which includes nozzle 52 and gun heater 54.
  • Powder particle diameter sizes can range from 1 to 120 microns, more specifically from 5 to 75 microns.
  • Pressurized gas is fed from gas pre-heater 56 to gun heater 54 through conduit 55.
  • Exemplary gases for use in the system include helium, nitrogen, or a mixture of helium and nitrogen. Helium can provide greater gas velocities than nitrogen and has the additional technical effect of being benefited by the nitriding process because unlike a nitrogen-based gas stream, helium does not provide any opportunity for nitriding to occur in the spray gun 50.
  • the powder and the gas streams are mixed in the gun and accelerated to supersonic speeds as the gas/powder mixture exits the nozzle 52.
  • the system also includes a controller or control console 58, which receives input from gun pressure sensor 60 and gun temperature sensor 62 and provides control signals to the gas pre-heater and powder feeder.
  • the term "cold” in “cold spray deposition” refers to the fact that the gas is maintained at a temperature below the melting point of the metal powder; however, as described above the gas is heated in both the gas pre-heater 56 and the gun heater 54.
  • the temperature of the gas used in the process can range from 0°C to 1200°C, more specifically from 200°C to 1000°C, and even more specifically from 200°C to 800°C.
  • Gas pressure can range from 5 bar to 60 bar, more specifically from 15 bar to 45 bar, and even more specifically from 20 bar to 40 bar.
  • Ti-6Al-4V alloy powder materials were nitrided in a fluidized bed reactor as shown in FIG. 1 .
  • the reactor was then placed in a Model K-3-18 reactor furnace (CM Furnaces, Inc.).
  • argon gas Praxair
  • the furnace temperature was increased at a rate of about 4.5°C/min to the target nitridation temperature as shown in Table 1.
  • a control sample was also prepared in which argon gas was used for the entire process without any nitrogen gas.
  • the gas flow was switched to nitrogen (Matheson) and the temperature was held for the times indicated in Table 1.
  • the gas flow was switched to argon and the reactor was allowed to cool down. This was done primarily to isolate the soak time and to prevent any further nitridation that might occur at the higher temperatures during the slow cooling process.
  • the powder temperature reached a low enough temperature (about 300°C)
  • the gas flow was switched again, back to nitrogen and the furnace continued to cool down to ambient temperature.
  • the resulting metal powders, along with samples of the untreated powder were characterized using scanning electron microscopy (SEM) and energy dispersive X-ray microanalysis (EDX).
  • nitridation at 700°C and 800°C each resulted in an increase in surface nitrogen on the particles and a decrease in surface oxygen for the particles, with nitridation at 800°C producing a greater effect than nitridation at 700°C.
  • Surface carbon detected by XPS is believed to result from surface contamination during preparation of the metal powders.
  • the metal powders were used in a system as shown in FIG. 2 using helium at 700° and 30 bar as the gas or a 50/50 blend of helium and nitrogen at 800°C and 40 bar.
  • the nitrided titanium alloy powders exhibited significantly reduced nozzle clogging (and resulting higher quality metal deposits) than either the untreated powder or the control powder.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)

Claims (15)

  1. Procédé d'application d'un métal comprenant du titane sur un substrat, le procédé comprenant :
    la nitruration de la surface de particules de poudre métallique (46) comprenant du titane par mise en contact des particules (46) avec un premier gaz comprenant de l'azote dans un réacteur à lit fluidisé ; et
    le dépôt des particules de poudre métallique (46) sur le substrat par dépôt par pulvérisation à froid à l'aide d'un second gaz.
  2. Procédé selon la revendication 1, dans lequel les particules de poudre métallique (46) comprennent au moins un titane ou un alliage de titane choisi parmi les classes 5 (Ti 6Al 4V) et 23 (Ti 6Al 4V), selon la norme ASTM B861-10.
  3. Procédé selon la revendication 2, dans lequel les particules de poudre métallique (46) comprennent au moins un titane ou un alliage de titane choisi parmi Ti 6Al 4V, Ti-3Al-2.5V, Ti-5Al-2.5Sn, Ti-8Al-1Mo-1V, Ti 6Al 2Sn 4Zr 2Mo, α+β Ti-6Al-4V, et quasi β Ti-10V-2Fe-3Al.
  4. Procédé selon l'une quelconque des revendications 1 à 3, dans lequel le premier gaz comprend au moins 1 % en volume d'azote.
  5. Procédé selon l'une quelconque des revendications 1 à 4, dans lequel le premier gaz est constitué essentiellement d'azote.
  6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel le réacteur à lit fluidisé fonctionne à une température située dans la plage allant de 500 °C à 850 °C.
  7. Procédé selon l'une quelconque des revendications 1 à 6, dans lequel le premier gaz est à une pression située dans la plage allant de 0,11 à 0,12 MPa.
  8. Procédé selon l'une quelconque des revendications 1 à 7, dans lequel la vitesse spatiale du premier gaz dans le réacteur à lit fluidisé se situe dans la plage allant de 1 min-1 à 30 min-1.
  9. Procédé selon l'une quelconque des revendications 1 à 8, dans lequel les particules de poudre métallique (46) sont mises en contact avec le premier gaz dans le réacteur à lit fluidisé (12) pendant au moins 1 minute.
  10. Procédé selon l'une quelconque des revendications 1 à 9, dans lequel le second gaz comprend de l'hélium.
  11. Procédé selon la revendication 10, dans lequel le second gaz comprend en outre de l'azote, ou dans lequel le second gaz est constitué essentiellement d'hélium.
  12. Procédé selon l'une quelconque des revendications 1 à 11, dans lequel le second gaz est à une température située dans la plage allant de 20 °C à 850 °C.
  13. Procédé selon l'une quelconque des revendications 1 à 3, dans lequel le premier gaz comprend au moins 1 % en volume d'azote,
    dans lequel le réacteur à lit fluidisé fonctionne à une température située dans la plage allant de 500 °C à 800 °C, plus préférablement encore de 600 °C à 750 °C, et plus préférablement encore de 600 °C à 700 °C,
    dans lequel la pression dans le réacteur peut se situer dans la plage allant de 0,11 à 0,12 MPa, plus préférablement de 0,11 MPa à 0,115 MPa,
    dans lequel les particules de poudre métallique (46) sont mises en contact avec le premier gaz dans le réacteur à lit fluidisé (12) pendant au moins 1 minute, plus préférablement de 1 minute à 30 minutes, plus préférablement de 1 minute à 10 minutes, et plus préférablement encore de 1 minute à 5 minutes, et
    dans lequel les particules de poudre métallique (46) après nitruration comprennent de l'azote à la surface des particules et comprennent également une partie interne de particule exempte d'azote.
  14. Procédé selon l'une quelconque des revendications 1 à 3 et 13, dans lequel le premier gaz comprend au moins 1 % en volume d'azote,
    dans lequel le réacteur à lit fluidisé fonctionne à une température située dans la plage allant de 500 °C à 800 °C, plus préférablement encore de 600 °C à 750 °C, et plus préférablement encore de 600 °C à 700 °C,
    dans lequel la pression dans le réacteur peut se situer dans la plage allant de 0,11 à 0,12 MPa, plus préférablement de 0,11 MPa à 0,115 MPa,
    dans lequel les particules de poudre métallique (46) sont mises en contact avec le premier gaz dans le réacteur à lit fluidisé (12) pendant au moins 1 minute, plus préférablement de 1 minute à 30 minutes, plus préférablement de 1 minute à 10 minutes, et plus préférablement encore de 1 minute à 5 minutes, et
    dans lequel les particules de poudre métallique (46) après nitruration présentent une teneur en azote en surface située dans la plage allant de 5,96 % en poids à 12,22 % en poids, telle que déterminée par spectroscopie de photoélectrons induite par rayons X.
  15. Procédé selon l'une quelconque des revendications 1 à 3, 13 et 14, dans lequel le premier gaz comprend au moins 1 % en volume d'azote,
    dans lequel le réacteur à lit fluidisé fonctionne à une température située dans la plage allant de 500 °C à 800 °C, plus préférablement encore de 600 °C à 750 °C, et plus préférablement encore de 600 °C à 700 °C,
    dans lequel la pression dans le réacteur peut se situer dans la plage allant de 0,11 à 0,12 MPa, plus préférablement de 0,11 MPa à 0,115 MPa,
    dans lequel les particules de poudre métallique (46) sont mises en contact avec le premier gaz dans le réacteur à lit fluidisé (12) pendant au moins 1 minute, plus préférablement de 1 minute à 30 minutes, plus préférablement de 1 minute à 10 minutes, et plus préférablement encore de 1 minute à 5 minutes, et
    dans lequel les particules de poudre métallique (46) après nitruration présentent un rapport azote: oxygène en % en poids en surface situé dans la plage allant de 5,96:26,2 à 12,26:16,75, tel que déterminé par spectroscopie de photoélectrons induite par rayons X.
EP16740623.0A 2015-01-21 2016-01-20 Procédé de pulvérisation à froid mettant en oeuvre une poudre métallique traitée Active EP3247516B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201562106140P 2015-01-21 2015-01-21
PCT/US2016/013995 WO2016118551A1 (fr) 2015-01-21 2016-01-20 Procédé de pulvérisation à froid mettant en œuvre une poudre métallique traitée

Publications (3)

Publication Number Publication Date
EP3247516A1 EP3247516A1 (fr) 2017-11-29
EP3247516A4 EP3247516A4 (fr) 2018-08-22
EP3247516B1 true EP3247516B1 (fr) 2019-08-28

Family

ID=56417666

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16740623.0A Active EP3247516B1 (fr) 2015-01-21 2016-01-20 Procédé de pulvérisation à froid mettant en oeuvre une poudre métallique traitée

Country Status (3)

Country Link
US (1) US20180002815A1 (fr)
EP (1) EP3247516B1 (fr)
WO (1) WO2016118551A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018047098A1 (fr) * 2016-09-07 2018-03-15 Tessonics, Inc Trémie avec microréacteur et cartouche pour pulvérisation à froid à basse pression
CN107377968A (zh) * 2017-09-08 2017-11-24 安徽工业大学 一种基于喷吹流化的异质复合粉末的制备装置及制备方法
US20190160528A1 (en) * 2017-11-27 2019-05-30 Hamilton Sundstrand Corporation Method and apparatus for improving powder flowability
CN109935533B (zh) * 2017-12-18 2021-09-21 无锡华润安盛科技有限公司 封装体的反应层去除装置及去除方法
US11097340B2 (en) 2018-11-19 2021-08-24 Hamilton Sundstrand Corporation Powder cleaning systems and methods
CN111992715A (zh) * 2020-08-21 2020-11-27 浙江工业大学 一种激光诱导界面原位反应增强的钛合金增材制造方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5149514A (en) * 1989-04-04 1992-09-22 Sri International Low temperature method of forming materials using one or more metal reactants and a halogen-containing reactant to form one or more reactive intermediates
SE9001009L (sv) * 1990-03-21 1991-09-22 Ytbolaget I Uppsala Ab Foerfarande foer att bilda ett haart och slitagebestaendigt skikt med god vidhaeftning paa titan eller titanregleringar och produkter, framstaellda enligt foerfarandet
WO1998051419A1 (fr) * 1997-05-13 1998-11-19 Richard Edmund Toth Poudres dures a revetement resistant et articles frittes produits a partir de ces poudres
US7232556B2 (en) * 2003-09-26 2007-06-19 Nanoproducts Corporation Titanium comprising nanoparticles and related nanotechnology
KR101171682B1 (ko) * 2010-04-19 2012-08-07 아주대학교산학협력단 저온 분사 방법을 이용한 알루미늄 또는 알루미늄 합금 표면의 질화처리방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
EP3247516A1 (fr) 2017-11-29
US20180002815A1 (en) 2018-01-04
EP3247516A4 (fr) 2018-08-22
WO2016118551A1 (fr) 2016-07-28

Similar Documents

Publication Publication Date Title
EP3247516B1 (fr) Procédé de pulvérisation à froid mettant en oeuvre une poudre métallique traitée
EP3488950B1 (fr) Procédé et appareil pour améliorer l'aptitude à l'écoulement de poudre
US8591986B1 (en) Cold spray deposition method
CN1120756C (zh) 用来对中空物件的复杂内表面进行气相镀敷的方法和装置
EP0911425B1 (fr) Procédé pour l'enduction de surfaces
AU2018286648B2 (en) Process for forming wrought structures using cold spray
TW202218774A (zh) 用於合成球狀金屬粉末之系統及方法
EP3254784B1 (fr) Procédé de revêtement de particules de poudre métallique avec silicium
Shahzad et al. Deposition of the Ti-Al coatings on different metallic substrates by mechanical alloying and subsequent laser treatment
CN115584486A (zh) 一种碳化钽涂层制品及制备方法
EP0924315B1 (fr) Production de gaz chaud pour la pulvérisation thermique
KR930007857B1 (ko) 산화아연위스커의 제조방법
US11692273B2 (en) Method for applying a titanium aluminide alloy, titanium aluminide alloy and substrate comprising a titanium aluminide alloy
US11753306B2 (en) Preparation of metal diboride and boron-doped powders
CN115637419A (zh) 一种钽-碳化钽复合涂层的制备方法及其制品
CN115786876A (zh) 一种利用cvd制备碳化钽涂层的方法及其制品
CN110158051B (zh) 一种低温介稳流化工艺制备TiOxCyNz涂层及其复合涂层的***及方法
Zhevtun et al. Micro-and nanoporous structure formed on the titanium surface by laser treatment
US20090042716A1 (en) High Temperature Reactor for the Poduction of Nanophase WC/CO Powder
KR100743188B1 (ko) 나노 조직의 고 경도 ＷＣ-Ｃｏ 코팅 제조 방법
CN106048497A (zh) 高γ‑TiAl相含量的耐磨损涂层及其制备方法
Yandouzi et al. Deposition and characterization of WC–Co coatings prepared by continuous-and pulsed-cold spray processes
PL243972B1 (pl) Sposób niskociśnieniowego natryskiwania na zimno powłok z proszków cząstek stałych i układ do niskociśnieniowego natryskiwania na zimno powłok z proszków cząstek stałych
Grant et al. Spray processing of Ti metal matrix composites
CN109750248A (zh) 一种γ-TiAl表面喷丸处理促进Al2O3膜热生长的方法及应用

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20170809

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20180725

RIC1 Information provided on ipc code assigned before grant

Ipc: C09K 3/18 20060101ALI20180719BHEP

Ipc: C22C 29/00 20060101ALI20180719BHEP

Ipc: B22F 1/02 20060101AFI20180719BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C09K 3/18 20060101ALI20190215BHEP

Ipc: C22C 29/00 20060101ALI20190215BHEP

Ipc: C22C 29/16 20060101ALI20190215BHEP

Ipc: C23C 8/24 20060101ALI20190215BHEP

Ipc: B22F 1/02 20060101AFI20190215BHEP

Ipc: C23C 8/80 20060101ALI20190215BHEP

Ipc: C23C 24/04 20060101ALI20190215BHEP

Ipc: B22F 1/00 20060101ALI20190215BHEP

INTG Intention to grant announced

Effective date: 20190307

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1171766

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190915

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602016019450

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20190828

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190828

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190828

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190828

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191128

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190828

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191128

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190828

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191230

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190828

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191228

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190828

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191129

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190828

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190828

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1171766

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190828

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190828

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190828

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190828

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190828

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190828

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190828

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190828

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190828

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190828

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200224

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602016019450

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG2D Information on lapse in contracting state deleted

Ref country code: IS

26N No opposition filed

Effective date: 20200603

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190828

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190828

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20200131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200120

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200131

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200131

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200120

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602016019450

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: B22F0001020000

Ipc: B22F0001000000

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190828

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190828

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190828

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230125

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20230120

Year of fee payment: 8

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230520

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20240129

Year of fee payment: 9

Ref country code: GB

Payment date: 20240129

Year of fee payment: 9