EP2791381A2 - Gaine de flamme ou enveloppe de gaz réactif pour procédés de pulvérisation de plasma en suspension - Google Patents

Gaine de flamme ou enveloppe de gaz réactif pour procédés de pulvérisation de plasma en suspension

Info

Publication number
EP2791381A2
EP2791381A2 EP12812461.7A EP12812461A EP2791381A2 EP 2791381 A2 EP2791381 A2 EP 2791381A2 EP 12812461 A EP12812461 A EP 12812461A EP 2791381 A2 EP2791381 A2 EP 2791381A2
Authority
EP
European Patent Office
Prior art keywords
plasma
liquid suspension
shroud
effluent
suspension
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.)
Granted
Application number
EP12812461.7A
Other languages
German (de)
English (en)
Other versions
EP2791381B1 (fr
Inventor
Christopher A. PETORAK
Don J. LEMEN
Albert Feuerstein
Thomas F LEWIS III
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.)
Praxair ST Technology Inc
Praxair Technology Inc
Original Assignee
Praxair ST Technology Inc
Praxair Technology Inc
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 Praxair ST Technology Inc, Praxair Technology Inc filed Critical Praxair ST Technology Inc
Priority to PL12812461T priority Critical patent/PL2791381T3/pl
Publication of EP2791381A2 publication Critical patent/EP2791381A2/fr
Application granted granted Critical
Publication of EP2791381B1 publication Critical patent/EP2791381B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • 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 invention relates to suspension plasma sprays, and more particularly to methods and systems for the shrouding of suspension plasma spray effluents and/or sheathing the injection of liquid suspensions using a reactive gas and/or flame envelope to facilitate and control the effluent and suspension interactions.
  • Conventional plasma spray technology primarily uses powder feeders to deliver powdered coating material into a plasma jet of a plasma spray gun.
  • this technology is typically limited to the use of particles of at least +350 mesh (i.e., a median particle size of approximately of 45 microns in which 50 percent of particles are smaller than the median size and the other 50 percent of the particles are larger than the median size) or larger.
  • particles of at least +350 mesh i.e., a median particle size of approximately of 45 microns in which 50 percent of particles are smaller than the median size and the other 50 percent of the particles are larger than the median size
  • fine particles tend to pack tightly and agglomerate, increasing the likelihood of clogging in conventional powder feed systems.
  • SPS Suspension plasma spray
  • the liquid serves as a carrier for the sub-micron size particles that would otherwise tend to agglomerate restricting or eliminating powder flow to the torch.
  • the liquid also has been shown to function as a thermally activated solution that precipitates solids or reacts with suspended particles. Due primarily to the use of very small particles suspended in the liquid carrier, the suspension plasma spray process has demonstrated the ability to create unique coating microstructures with distinctive properties.
  • the liquid droplets also provide the additional mass to impart the momentum necessary for entrainment by radial injection.
  • the finer particulate size of the coating constituents have increased surface areas that can rapidly heat up and cool down at faster rates than typically encountered in standard plasma technology. Accordingly, the increased surface area of the finer particulates creates unprecedented challenges to optimizing the correct stand-off distance.
  • the present embodiments of the invention addresses some of the disadvantages and provides techniques to control the aforementioned interactions through use of a reactive gas shroud surrounding the plasma effluent stream and liquid suspension contained therein (collectively, referred to as "effluent,” “effluent stream,” “plasma,” or “plasma effluent,” or “plasma effluent stream” herein and throughout the specification).
  • the present invention uniquely combines a reactive gas shroud with a plasma spray process using submicron particles delivered via liquid suspension to improve current suspension plasma spray capabilities and create new coating microstructure possibilities through controlling the suspension injection and fragmentation as well as the interactions between the effluent and suspensions.
  • the invention may include any of the following aspects in various combinations and may also include any other aspect described below in the written description or in the attached drawings.
  • the present invention may be characterized as a thermal spray system for producing coatings on a substrate from a liquid suspension
  • a thermal spray torch for generating a plasma
  • a liquid suspension delivery subsystem for delivering a flow of the liquid suspension with sub-micron particles
  • a nozzle assembly for delivering the plasma from the thermal spray torch to the liquid suspension to produce a plasma effluent
  • the nozzle assembly adapted for producing a reactive gas shroud substantially surrounding said plasma effluent; the reactive gas shroud configured to substantially retain entrainment of the sub-micron particles in the plasma effluent and substantially inhibit gases from entering and reacting with the plasma effluent; wherein the reactive gas shroud reacts with the plasma effluent to enhance fragmentation of the suspension droplets and create evaporative species of the sub-micron particles within the plasma effluent.
  • the present invention may also be characterized as a method of producing coatings on a substrate using a liquid suspension with sub-micron particles dispersed therein, the method comprising the steps of: generating a plasma from a thermal spray torch; delivering a flow of liquid suspension with sub-micron particles dispersed therein to the plasma or in close proximity thereto to produce a plasma effluent stream;
  • a reactive gas shroud to keep the sub-micron particles entrained within the plasma effluent and substantially prevent entrainment of ambient gases into the plasma effluent; reacting the shroud gas with the plasma effluent to enhance fragmentation of the suspension droplets and create evaporative species of the sub-micron particles within the plasma effluent; and directing the shrouded plasma effluent with the sub-micron particles contained therein towards the substrate to coat the substrate.
  • FIG. 1 is a schematic illustration of a prior art suspension plasma spray process employing an axial injection of the liquid suspension
  • FIG. 2 is a schematic illustration of a prior art suspension plasma spray process employing an internal radial injection of the liquid suspension
  • FIG. 3 is a schematic illustration of a prior art suspension plasma spray process employing an external radial injection of the liquid suspension
  • FIG. 4 is a schematic illustration of a reactive gas shroud of a suspension plasma spray process employing an axial injection of the liquid suspension in accordance with an embodiment of the present invention
  • FIG. 5 is a schematic illustration of a reactive gas shroud of a suspension plasma spray process employing an internal radial injection of the liquid suspension in accordance with another embodiment of the present invention
  • FIG. 6 is a schematic illustration of a reactive gas shroud of a suspension plasma spray process employing an external radial injection of the liquid suspension in accordance with yet another embodiment of the present invention
  • FIG. 7 shows yet another embodiment of the present invention employing a dual gas shroud consisting of an inner reactive gas layer and an outer inert gas shield surrounding a suspension plasma spray process;
  • FIG. 8 shows yet another embodiment of the present invention employing a dual gas shroud consisting of a first reactive gas layer and a second reactive gas layer surrounding a suspension plasma spray process;
  • FIG. 9 is a schematic illustration of an suspension plasma spray process employing a gas shrouded or gas sheathed axial injection of the liquid suspension in accordance with an embodiment of the present invention
  • FIG. 10 is a schematic illustration of a suspension plasma spray process employing a gas shrouded or gas sheathed internal radial injection of the liquid suspension in accordance with another embodiment of the present invention.
  • FIG. 11 is a schematic illustration of a suspension plasma spray process employing a gas shrouded or gas sheathed external radial injection of the liquid suspension in accordance with yet another embodiment of the present invention.
  • the present disclosure relates to a novel SPS system and process for the deposition of coating material.
  • the SPS system and process of the present invention is particularly suitable for deposition of sub-micron particles.
  • the disclosure is set out herein in various embodiments and with reference to various aspects and features of the invention.
  • FIGS. 1 -3 show several schematic illustrations of prior art suspension plasma spray systems and processes 100, 200 and 300 employing an axial injection of the liquid suspension; internal radial injection of the liquid suspension and external radial injection of the liquid suspension, respectively.
  • Figures 1 and 2 show fragmentation of the liquid carrier occurs at regions 1 10 and 201 in an undesirable random-like manner due to the turbulent flow in the effluent. The fragmentation occurs soon after the plasma effluent and liquid suspension are in contact.
  • the term "effluent” and "plasma effluent” will be used interchangeably and are intended to refer to any combination of the plasma gas, coating constituents or particles and liquid carrier, each of which is flowing from the outlet of a torch nozzle.
  • the effluent 140, 240 and 340 will more than likely consist of plasma (i.e., hot primary torch gas ionized by virtue of being exposed to an arc generated between the cathode and anode) and droplets of liquid carrier containing coating particles (i.e., liquid suspension 109, 209 and 309).
  • the effluent 140, 240 and 340 will primarily consist of the coating particulates and a potentially significantly cooler effluent 140, 240 and 340, as substantially all of the liquid carrier has evaporated by this stage of the SPS coating process 100, 200 and 300.
  • Figures 1 and 2 also show that a portion of the fragmented droplets of the liquid suspension 109 and 209 are ejected from the effluent 140 and 240 at regions 1 10 and 210, respectively.
  • Figures 1 -3 further show atmospheric entrainment 122, 222 and 322 into the plasma effluent 140, 240 and 340 in a region that is in close proximity to the outlet of the torch nozzle 105, 205 and 305.
  • Figure 1 shows there is evaporation of the liquid carrier, as shown by representative region 105, causing many of the sub-micron solid particles to coalesce and melt.
  • Figures 1-3 further show that as the effluent stream 140, 240 and 340 approaches the substrate 108, 208 and 308 to be coated, the temperature profile within the effluent stream 140, 240 and 340 changes resulting in some re-solidification of cooler particles and condensing of entrained evaporated species. Upon reaching the
  • the coating material in the various physical states impact the substrate and form a coating 106, 206 and 306, including the physical bonding of coating material to the substrate. Adverse chemical reactions between the substrate 108, 208 and 308 and the coating materials can occur.
  • the present embodiments of the invention address many of the aforementioned disadvantages shown in Figures 1 -3.
  • the present invention provides techniques to control the aforementioned adverse interactions through use of a reactive gas shroud and/or sheath surrounding the effluent stream and/or injection location for liquid suspension.
  • SPS system and process 400 employs an axial injection of the liquid suspension 409 with an extended reacted gas shroud 401 surrounding the effluent 440 (i.e., plasma and liquid suspension 409).
  • Any suitable reactive gas may be used to create the reacted gas shroud 401 , such as, for example, oxygen, hydrogen carbon dioxide; hydrocarbon fuels and in some instances nitrogen or combinations thereof.
  • reactive gas shroud 401 the effluent440 and suspension 409 interaction can be more precisely controlled to create new coating microstructure possibilities as a result of the chemical reactions occurring between the suspension 409 and the reactive gas shroud 401.
  • FIG. 4 shows that the shroud 401 is created by flowing reacted gas at a predetermined flow rate through an outer nozzle that surrounds an inner nozzle through which the liquid suspension 409 and primary torch gas 416 can sequentially or co-flow relative to each other.
  • the shroud 401 is oriented around the flow of effluent 402, thereby forming a protective envelope of reactive gas that surrounds the effluent 440.
  • Figure 4 shows that the shroud 401 extends continuously from within the nozzle 405 of the torch to the substrate surface 408 to create a completed envelope of the effluent 440 contained therein.
  • a plasma 419 is created as primary torch gas 416 flows between a cathode 412 and anode 413 into a region where an arc is generated.
  • the carrier gas transports the liquid suspension 409 and is shown flowing with the liquid suspension 409 through the center of the nozzle 405.
  • An arc is generated between the cathode 412 and anode 413.
  • the primary torch gas 416 passes through the arc region and ionizes into a hot plasma 419 of gaseous ions and/or radicals within the nozzle 405.
  • the plasma 419 provides the thermal energy source required to evaporate the liquid carrier and melt the coating constituents 415 of liquid suspension 409 as the effluent 440 flows towards the substrate surface 408.
  • the plasma 419 also provides the energy source to provide sufficient momentum to accelerate the coating constituents or particles 415 towards the substrate surface 408.
  • the liquid suspension 409 i.e., liquid carrier droplets with coating constituents 415 contained therein
  • plasma 419 emerge from the outlet of the nozzle 405 as an effluent 440.
  • the shrouded gas 401 converges within a throat section of the nozzle 405 and thereafter emerges from the nozzle 405. It should be understood that the terms "shroud” and “shrouded gas” have the same meaning and will be used herein and throughout the specification interchangeably.
  • the reactive gas shroud 401 is an oxygen- containing gas, such as, for example, oxygen gas or an oxygen diluted mixture of gases.
  • the oxygen-containing reactive gas shroud 401 can be used to control or increase the degree of mixing and spatial location of the mixing of the reactive gas 401 with the effluent 440, thus more precisely controlling the degree and location of the combustion with the effluent 440 and resulting thermal energy profile.
  • Enhanced combustion or other thermal reactions also can improve the fragmentation of the droplets of the liquid suspension 409 as well as evaporation of the sub-micron coating particles 415 within the suspension 409.
  • the oxygen-containing reactive gas shroud 401 can be used with a fuel based liquid carrier to produce more complete combustion which can be initiated or effected further upstream or closer to generation of the plasma source 419 than would occur with a non-shrouded spray process or traditional inert gas shroud around the plasma spray effluent.
  • the embodiment of Figure 4 demonstrates that advancing the combustion process further upstream toward the plasma source 419 would enable use of lower power plasma torches to both melt and evaporate the sub-micron particles 415 within the liquid carrier through more efficient use of the plasma stream's thermal energy.
  • the reactive gas shroud 401 is configured to flow at a sufficient flow rate relative to that of the effluent 440 so as to form a continuous envelope about the effluent 440.
  • the effluent 440 is characterized as having a trajectory or flow path of the liquid suspension 409 defined, at least in part, from the outlet of the nozzle 405 to the substrate surface 408, whereby the flow path is partially or fully enveloped by the reactive shroud 401.
  • the length of the reactive shroud 401 extends from the outlet of the nozzle 405 to the substrate surface 408 to fully surround the effluent 440.
  • the continuous envelope of the shroud 401 creates a thermal envelope that acts as an effective insulator to retain heat in the effluent stream 440 across longer flow path distances from the outlet of the nozzle 405 to the surface of the substrate 408.
  • the controlled temperature from the outlet of the torch 405 to the substrate 408 enables evaporation of the liquid carrier of the liquid suspension 409.
  • the heat used to evaporate the liquid carrier is now realized by the coating constituents 415 generally contained within the droplets of the liquid suspension 409, which are now free floating and travelling towards the substrate surface 408.
  • the coating constituents 415 partially or substantially melt without undergoing significant cool down as they flow towards the surface of the substrate 408.
  • the molten coating constituents 415 impact the substrate surface 408 to deposit as a coating 403.
  • the improved thermal envelope therefore improves deposition efficiency.
  • the retention of heat within the effluent 440 creates improved uniformity in temperature distribution that can decrease stand-off working sensitivity.
  • the present invention as shown in the embodiment of Figure 4 allows a unique SPS system and process 400 for coating complicated geometries at father stand-off distances than previously attainable with conventional SPS, without incurring substantial solidification of the coating constituents 415 as they impact the substrate surface 408.
  • the use of the reactive gas shroud 401 around the plasma effluent 440 operates to create and/or retain more heat in the effluent 440 providing a larger operation envelope for the coating process.
  • the larger operational envelope translates to longer working distances between torch nozzle 405 and substrate 408 as well as better thermal treatment of the sub-micron particles 415.
  • the sub- micron particles 415 along its flow path trajectory are maintained at the prescribed operating temperatures for longer residence times resulting in improved melting and an increase in the evaporative species of the particles within the plasma effluent 440.
  • Use of reactive gas shroud 401 also facilitates control of the environment and temperatures near the substrate surface 408.
  • the reactive gas shroud can be configured in a controlled manner.
  • the most likely means of control involve adjusting or manipulating the flow characteristics of the reactive gas shrouds, including the volumetric flow rate and/or velocity of the gas shroud as well as concentrations of the reactive elements in the reactive gas shrouds.
  • the turbulence and dispersion characteristics of the reactive gas shroud may also be controlled. Many of these flow characteristics are dictated by the geometry and configuration of the nozzle or nozzles used to form the reactive gas shrouds as well as the reactive shroud gas supply pressures and temperatures.
  • FIG. 4 shows that the shrouded gas 401 is configured to flow in a laminar flow rate regime.
  • the controlled and lowered velocity of the laminar flowing shroud 401 can enable the fragmentation phenomena of the droplets of the liquid suspension 409 across the shroud 401 to occur in a more controlled manner compared to conventional SPS systems and processes 100, 200 and 300 of Figs. 1 -3.
  • the fragmented droplets of liquid suspension 409 therefore attain an improved uniformity in size distribution.
  • the coating constituents 415 deposit on the substrate surface 408 to form a coating 403 having a more controlled particle size distribution.
  • the shroud 401 also counteracts any tendency for droplets of the liquid suspension 409 to eject from the effluent 440.
  • the effluent 440 is in a turbulent flow regime which may be sufficient to break up liquid droplets into smaller droplets, and in the process of doing so, undesirably impart excessive momentum to at least some of the droplets to eject them from the effluent stream 440.
  • Employing the shroud 401 can facilitate the retention of the droplets of the liquid suspension 409 and coating constituents 415 within the effluent 440. As a result, increased utilization of the coating constituents 415 is attained.
  • the combination of the aforementioned process benefits can produce a coating 403 deposited onto the substrate surface 408 having a micro structure with grain orientation and sufficiently small particle size distribution.
  • the favorable micro structural possibilities are controllable and reproducible by virtue of the innovative SPS system and process 400.
  • Figure 5 shows an SPS system and process 500 in which the liquid suspension 509 is internally injected within the torch nozzle 505.
  • the internal injection of the liquid suspension 509 can occur in a substantially radial direction at an orthogonal orientation with respect to the axis of the plasma 519 that is generated within the nozzle 505 between the cathode 512 and anode 513. It should be understood that the angle of injection of the liquid suspension 509 relative to the plasma 519 may be varied.
  • Figure 5 shows that the primary torch gas 516 passes through the arc region and ionizes into a hot plasma state 519 of gaseous ions within the nozzle 505.
  • the liquid suspension 509 is internally injected into the plasma region 519 It should be understood that injection of suspension 509 can occur downstream of the plasma 519 within the anode, which may represent a region where the torch gas 516 has cooled down from the plasma state to a superheated gas.
  • the turbulent flow of the plasma 519 fragments and/or atomizes the liquid carrier droplets of suspension 509 within the nozzle 505 and also at the outlet of the nozzle 505.
  • the length of the reactive shroud 501 extends in a continuous manner from the outlet of the nozzle 505 to the substrate surface 508.
  • the shroud 501 provides heat retention to create a continuous thermal envelope and also prevents ejection of the droplets of suspension 509 from the effluent 540.
  • the embodiment of Figure 5 shows that the shrouded reactive gas 501 is configured to flow in a laminar flow rate regime.
  • the controlled and lowered velocity of the laminar flowing shroud 501 can enable the fragmentation phenomena of the droplets of the liquid suspension 509 across the shroud 501 to occur in a more controlled manner compared to conventional SPS systems and processes 100, 200 and 300 of Figs. 1-3.
  • the fragmented droplets of liquid suspension 509 therefore attain an improved uniformity in size distribution.
  • the coating constituents 515 deposit on the substrate surface 508 to form a coating 503 having a more controlled particle size distribution.
  • certain coating applications may not require substantial fragmentation of the droplets of liquid suspension 509.
  • the shroud 501 can be configured to not fragment the droplets yet still achieve the other benefits of utilizing a shroud 501 that have been mentioned above.
  • Figure 6 shows an SPS system and process 600 in which the liquid suspension 609 is injected externally to the torch nozzle 605.
  • the external injection of the liquid suspension 609 can occur in a substantially radial direction at an orthogonal orientation with respect to the axis of the plasma effluent 640.
  • the angle of injection of the liquid suspension 609 relative to the plasma effluent 640 may be varied.
  • the reactive shrouded gas 601 is configured to flow in a laminar flow rate regime to produce more uniform fragmentation of the droplets of the liquid suspension 609.
  • FIG. 7 is a schematic illustration of another embodiment of the present invention employing a dual gas shroud consisting of an inner reactive gas shroud layer 701 and an outer inert gas shield 702 surrounding a suspension plasma spray process 700.
  • the inner reactive gas shroud layer 701 is preferably laminar flowing, as shown in Figure 7.
  • Use of the dual shroud in this specific arrangement may further improve heat retention within the region that the effluent 740 flows within, particle fragmentation of the droplets and temperature uniformity along the substrate 708.
  • the dual shroud also can improve confinement of the coating particulates 715 within the effluent 740 along the flow path, thereby substantially reducing or eliminating coating particulate 715 ejection from the effluent 740. As a result, increased deposition efficiency on the substrate 708 is attained.
  • Fig. 8 shows a dual reactive gas shroud consisting of a first inner reactive gas shroud layer 802 and a second outer reactive gas shroud layer 801 surrounding a suspension plasma spray process 800.
  • the first inner reactive gas shroud layer 802 is preferably laminar flowing, as shown in Figure 8.
  • the dual reactive gas shroud has two reactive shrouds.
  • Each of the reactive gas shrouds 801 and 802 is independently controlled (e.g., the flow rates are independently controlled).
  • the gases used for the reactive gas shrouds 801 and 802 may be the same or different.
  • the presence of two reactive shrouds or shields that are independently controlled can help improve combustion reactions along the flow path of the effluent 840.
  • other chemical reactions may be facilitated with the use of a dual reactive shroud gas in which each of the reactive gas shrouds 801 and 802 preferentially react with specific elements or compounds in the liquid suspension 809 resulting in a chemical reaction that occurs spontaneously or occurs due to the thermal energy of the plasma effluent 840.
  • Such chemical reactions can be designed and controlled to yield improvements in the chemical composition, physical property or micro structure of the deposited coating 803.
  • the inert gases typically include argon, nitrogen, and helium or combinations thereof.
  • the reactive gas shroud can be employed.
  • two or more reactive gas shrouds can be configured, preferably independent of each other, to surround an effluent.
  • two or more reactive gas shrouds in combination with an inert gas shroud can be employed.
  • the inert gas shroud can be configured between the reactive gas shrouds.
  • the inert gas shroud can be arranged so as to surround all of the reactive gas shrouds.
  • the inert gas shroud or shield can be positioned within each of the reactive gas shrouds.
  • a reactive gas shroud may also be selectively configured so as to only surround only a portion of the effluent along its flow path towards the substrate.
  • the process benefits can translate into more controlled microstructures of deposited coatings.
  • parameters which determine the micro structure and properties of the coatings include the temperature, size and velocity of the coating constituents or particles and the extent to which the particles have reacted with or exposed to the surrounding environment during deposition.
  • the reactive gas shroud can retain heat and create a more uniform temperature and controlled temperature distribution as the coating particles impact the substrate surface. Additionally, the laminar flow reactive gas shrouds can help create more uniformly fragmented coating particles. The shrouded effluent therefore creates an improved microstructure.
  • Additional factors impacting the microstructure and properties of the deposited coatings include the rate of deposition, angle of impact, and substrate properties, each of which can be controlled to a greater degree, by virtue of the shroud. Since the coating constituents or particles are heated and accelerated by the gaseous effluent of the plasma, the temperature and velocity of the coating particles are a function of the physical and thermal characteristics of the effluent stream and the standoff distance between the exit of the plasma spray device and the substrate. By controlling the properties of the effluent stream by use of the shroud, the temperature and velocity of the coating particles can be controlled with greater precision to improve coating adhesion and coating microstructure.
  • a specific type of reactive gas shroud which can be employed in the present invention is a flame envelope surrounding the liquid suspension at or near the injection point.
  • Figs. 9 through 1 1 there are shown schematic illustrations of different embodiments of the configuration of a flame envelope, namely depictions of suspension plasma spray systems and processes employing a flame envelope shrouding the axial injection of the liquid suspension; a flame envelope shrouding an internal radial injection of the liquid suspension; and a flame envelope shrouding an external radial injection of the liquid suspension, respectively.
  • the term "flame envelope” as used herein and throughout the specification means a combusting flow formed by the combustion of a fuel and an oxidant which extends along the axis of the injected suspension stream.
  • Fig. 9 shows a suspension plasma spray system and process 900 employing a flame envelope 910 shrouding the axial injection of the liquid suspension 909.
  • the flame envelope 910 extends from the distal end of the injection nozzle 905 or nozzle face up to a point where the plasma 919 is generated between the cathode 912 and the anode 913. It should be understood that the flame envelope 910 can extend the entire length of the suspension stream being injected from out of the nozzle 905(i.e., extends from the nozzle face to the entry point in the plasma effluent).
  • the flame envelope 910 can provide sufficient thermal energy to evaporate the liquid droplets prior to exiting nozzle 905.
  • dry sub-micron coating particulates 915 can be introduced as the effluent 940 without agglomeration and without clogging in the injector.
  • the flame envelope 910 can also provide sufficient kinetic energy to improve fragmentation of the droplets of the suspension 909 and coating particle 915 size distribution.
  • Fig. 10 shows an alternative suspension plasma spray system and process
  • the flame envelope 1010 shrouding the radial injection of the liquid suspension 1009.
  • the flame envelope 1010 extends along the injector of the liquid suspension 1009 and can evaporate the liquid droplets prior to being introduced into the effluent 1040.
  • the flame envelope 1010 can also impart sufficient kinetic energy to the droplets of suspension 1009, thereby improving fragmentation and coating particle 1015 size distribution.
  • the flame envelope may also be configured external of the nozzle as shown in Figure 1 1.
  • Figure 1 1 shows a suspension plasma spray system and process 1 100 employing a flame envelope 1 1 10 shrouding the radial injection of the liquid suspension 1 109.
  • the flame envelope 1 1 10 extends along the injector of the liquid suspension 1 109 and can evaporate the liquid droplets prior to being introduced into the plasma effluent 1 1 19.
  • the flame envelope 1 1 10 can also impart sufficient kinetic energy to the droplets of suspension 1 109, thereby improving fragmentation and coating particle 1015 size distribution.
  • the flame envelope 910, 1010 and 1 1 10 serves several functions.
  • the flame envelope 910, 1010 and 1 1 10 can function as a shroud for the liquid suspension 909, 1009 and 1 109 that prevents the entrainment of ambient gases into the injected suspension stream 909, 1009 and 1 109 and thereby inhibits unwanted physical and chemical reactions such as oxidation of the sub-micron particles contained within the suspension 909, 1009 and 1 109.
  • Preventing entrainment of ambient gases also inhibits velocity decay of the suspension injection and allows the liquid suspension 909, 1009 and 1 109 with the sub- micron particles contained therein to penetrate into the plasma 919, 1019 and 1 1 19 with substantial retention of the injection velocity.
  • the flame envelope 910, 1010 and 1 1 10 also functions as a reactive shroud or partially reactive shroud that, when properly controlled, can initiate desired reactions within their respective liquid suspensions 909, 1009 and 1 109 or between the suspension 909, 1009 and 1 109 and the shroud gases at or near the point of injection.
  • the liquid carrier is a fuel, such as ethanol
  • the flame envelope initiates the combustion reaction of the liquid carrier which increases both the thermal and kinetic energy of the injection event proximate the entry to the plasma effluent. This additional thermal and kinetic energy causes improved fragmentation of the droplets as well as enhanced melting or evaporation of the sub-micron particles in the suspension before they reach the plasma effluent.
  • the flame envelope provides an energy source to evaporate the liquid carrier and melt, partially melt or even evaporate the suspended particles prior to entrainment into the plasma effluent.
  • the disclosed flame envelope surrounding the suspension injection stream enables an SPS system employing delivery of a suspension but entrainment or injection of a dry submicron particle into the plasma effluent similar to APS powder injection, but at the sub-micron particle size.
  • the flame envelope surrounding the suspension injection stream enables an SPS system employing delivery of a suspension but entrainment or injection of melted sub-micron particles into the plasma effluent, the injection of evaporated species of the sub-micron particles into the plasma effluent.
  • the disclosed flame envelope surrounding the suspension injection stream enables an SPS system employing delivery of a liquid suspension with entrainment or injection of highly fragmented suspension droplets into the plasma effluent.
  • the disclosed flame envelope or reactive shroud surrounding the injection stream enables delivery of a liquid suspension wherein the sub-micron particles are reacted in-situ to form the desired ceramic or cermet coating materials which are entrained into the plasma effluent.
  • each of the above-described delivery, injection and entrainment techniques allows more precise control of the average particle size and particle size distribution injected or entrained into the effluent and subsequently impacting the substrate to provide the desired coating microstructures.
  • the use of a flame envelope or reactive shroud surrounding the suspension injection enables new choices or design options for the composition of the SPS liquid suspensions, including make-up of the liquid carriers and particle characteristics.
  • the flame envelope or reactive sheath/shroud surrounding the liquid suspension injection in reference to the Figures has the potential to provide additional thermal and kinetic energy to the SPS spray process, the present system and method would enable use of lower power plasma torches in an SPS process and a more efficient use of the thermal energy in the plasma stream. Also, the use of the presently disclosed flame envelope or reactive sheath/shroud surrounding the liquid suspension injection provides opportunities to further control and enhance the entire SPS process including: delivery or handling of the suspension; creating of the plasma jet; injection or entraining the coating materials into the plasma jet; and delivery/impact of the coating materials onto the substrate to be coated.
  • the injection of the coating materials into the plasma jet is preferably controlled so as to reach the optimized location within the effluent and with reduced interaction by effluent flow at the point of injection.
  • a portion of effluent at or near the point of suspension injection can be deflected to allow the sub-micron particles in either dry powder for, partially melted form, melted form and/or evaporative form to extend further into the effluent stream in a controlled and uniform manner
  • the flame envelope or sheath/shroud is employed as part of the SPS process merely to inhibit entrainment of ambient gases into the injected suspension and to allow the liquid suspension to penetrate deeply into the plasma effluent stream, the sheath/shroud is likely to promote further fragmentation of the suspension into droplets in controlled manner and location.
  • the flame envelope or reactive gas shroud aids in the control of the droplet size and droplet size distribution of the suspension being injected into the plasma effluent. In this manner, there is less fragmentation occurring in the plasma effluent and droplet size and droplet size distribution will be generally independent of spatial and temporal changes occurring as the plasma effluent moves toward the substrate to be coated. In other words, the droplet size and droplet size distribution is more precisely controlled resulting in improved plasma spray process control and improved coating microstructures
  • Fig. 9 shows another embodiment of the present invention employing a combustion flame shroud surrounding a suspension plasma spray process.
  • the typical reactive gases used for the reactive gas shroud include oxygen, hydrogen, carbon dioxide; hydrocarbon fuels, and nitrogen or combinations or combinations thereof.
  • the present invention is capable of depositing a wide array of fine particulate sizes in the sub-micron range, previously not possible by coating technologies, including that of conventional plasma spraying.
  • the SPS system and process of the present invention can deposit coating particulates below 100 nm.
  • the present invention can deposit coating particulates ⁇ or lower, without incurring undesirable agglomeration of the fine particulates as typically encountered in conventional spray systems and processes.
  • the SPS system described herein can be prepared utilizing suitable torch and nozzle assemblies that are commercially available, thus enabling and simplifying the overall fabrication process. Aspects of plasma generation can be carried out using standard techniques or equipment.
  • the liquid suspension source is a dispenser for the liquid suspension.
  • the source typically includes a reservoir, transport conduit (e.g., tubing, valving, and the like), and an injection piece (e.g., nozzle, atomizer and the like).
  • the liquid suspension delivery subsystem may contain measurement feedback of the process (e.g., flow rate, density, temperature) and control methods such as, for example, pumps and actuators that can work in conjunction or independently from one another.
  • the system may also contain additional flushing or cleaning systems, mixing and agitation systems, heating or cooling systems as known in the art.
  • the present invention thus provides a system and method for reactive gas shrouding of suspension plasma sprays and/or flame sheathing of liquid suspensions. While the invention herein

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Nozzles (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Plasma Technology (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention concerne un système et un procédé pour produire des revêtements de pulvérisation thermiques sur un substrat à partir d'une suspension liquide. Le système et le procédé décrits comprennent un pistolet de pulvérisation thermique pour générer un plasma et un sous-système de distribution de suspension liquide pour distribuer un flux de suspension liquide avec des particules submicroniques au plasma pour produire un effluent de plasma. Le sous-système de distribution de suspension liquide comprend un injecteur ou une buse qui peut produire une enveloppe de gaz réactif autour de l'effluent de plasma. Une enveloppe de flamme peut également être utilisée pour isoler l'injection de la suspension liquide. L'enveloppe ou l'enveloppe de flamme peut retenir les particules submicroniques entraînées à l'intérieur de l'effluent de plasma et sensiblement prévenir l'entraînement de gaz ambiant à l'intérieur de l'effluent de plasma. Le sous-système de distribution de suspension liquide peut être agencé comme un système d'injection axial, un système d'injection interne radial ou un système d'injection radial externe.
EP12812461.7A 2011-12-14 2012-12-14 Gaine de flamme ou enveloppe de gaz réactif pour procédés de pulvérisation de plasma en suspension Active EP2791381B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL12812461T PL2791381T3 (pl) 2011-12-14 2012-12-14 Osłona gazu reaktywnego lub powłoka płomienia do stosowania w procesach natryskiwania plazmowego z zawiesin

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US201161570532P 2011-12-14 2011-12-14
US201161570516P 2011-12-14 2011-12-14
PCT/US2012/069807 WO2013090754A2 (fr) 2011-12-14 2012-12-14 Gaine de flamme ou enveloppe de gaz réactif pour procédés de pulvérisation de plasma en suspension

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EP2791381A2 true EP2791381A2 (fr) 2014-10-22
EP2791381B1 EP2791381B1 (fr) 2018-10-17

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US (1) US20130156968A1 (fr)
EP (1) EP2791381B1 (fr)
JP (1) JP6165771B2 (fr)
KR (1) KR102106179B1 (fr)
CN (1) CN104114738B (fr)
CA (1) CA2859040C (fr)
MX (1) MX360218B (fr)
PL (1) PL2791381T3 (fr)
RU (1) RU2014128544A (fr)
SG (1) SG11201403108RA (fr)
TR (1) TR201819010T4 (fr)
WO (1) WO2013090754A2 (fr)

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US9752223B2 (en) * 2014-03-10 2017-09-05 United Technologies Corporation Equipment for plasma spray with liquid injection
CA2924476A1 (fr) * 2015-04-01 2016-10-01 Rolls-Royce Corporation Revetement a projection de plasma en condition de vide comportant des dispersions d'oxyde
WO2016210336A1 (fr) * 2015-06-24 2016-12-29 Khalifa University of Science, Technology & Research Flammes manipulées électrostatiquement pour une production de chaleur compacte
US20180166311A1 (en) * 2016-12-12 2018-06-14 Applied Materials, Inc. New repair method for electrostatic chuck
US20220285134A1 (en) * 2019-08-23 2022-09-08 Lam Research Corporation Near netshape additive manufacturing using low temperature plasma jets
CN114086107B (zh) * 2021-12-28 2023-07-14 河北复朗施纳米科技有限公司 一种纳米抑菌涂层装置
US20230366074A1 (en) * 2022-05-16 2023-11-16 Andrei V. Ivanov Oxygen Interception for Air Plasma Spray Processes

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Also Published As

Publication number Publication date
US20130156968A1 (en) 2013-06-20
MX2014007179A (es) 2014-11-25
EP2791381B1 (fr) 2018-10-17
KR20140106655A (ko) 2014-09-03
MX360218B (es) 2018-10-25
JP2015507691A (ja) 2015-03-12
CA2859040A1 (fr) 2013-06-20
RU2014128544A (ru) 2016-02-10
PL2791381T3 (pl) 2019-09-30
TR201819010T4 (tr) 2019-01-21
JP6165771B2 (ja) 2017-07-19
CA2859040C (fr) 2018-01-02
CN104114738B (zh) 2017-05-17
CN104114738A (zh) 2014-10-22
WO2013090754A3 (fr) 2013-08-08
KR102106179B1 (ko) 2020-04-29
SG11201403108RA (en) 2014-09-26
WO2013090754A2 (fr) 2013-06-20

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