WO2018154599A1 - An improved gas dynamic cold spray device and method of coating a substrate - Google Patents

An improved gas dynamic cold spray device and method of coating a substrate Download PDF

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Publication number
WO2018154599A1
WO2018154599A1 PCT/IN2018/050089 IN2018050089W WO2018154599A1 WO 2018154599 A1 WO2018154599 A1 WO 2018154599A1 IN 2018050089 W IN2018050089 W IN 2018050089W WO 2018154599 A1 WO2018154599 A1 WO 2018154599A1
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Prior art keywords
gas
powder
alloys
control panel
spray gun
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PCT/IN2018/050089
Other languages
French (fr)
Inventor
Naveen Manhar CHAVAN
Sorimuthu Kumar PILLAI
Sudharshan Phani Pardhasaradhi
Srinivasa Rao DAMERACHARLA
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International Advanced Research Centre For Powder Metallurgy And New Materials (Arci)
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Application filed by International Advanced Research Centre For Powder Metallurgy And New Materials (Arci) filed Critical International Advanced Research Centre For Powder Metallurgy And New Materials (Arci)
Priority to CN201880013832.3A priority Critical patent/CN110325282A/en
Priority to RU2019129866A priority patent/RU2744008C1/en
Priority to CA3054112A priority patent/CA3054112A1/en
Publication of WO2018154599A1 publication Critical patent/WO2018154599A1/en

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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/02Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05BSPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/14Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas designed for spraying particulate materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05BSPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/14Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas designed for spraying particulate materials
    • B05B7/1481Spray pistols or apparatus for discharging particulate material
    • B05B7/1486Spray pistols or apparatus for discharging particulate material for spraying particulate material in dry state
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C24/00Coating starting from inorganic powder
    • C23C24/02Coating starting from inorganic powder by application of pressure only
    • C23C24/04Impact or kinetic deposition of particles
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06Metallic material
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06Metallic material
    • C23C4/08Metallic material containing only metal elements

Definitions

  • the present invention relates to an improved gas dynamic cold spray device, a system and method of coating by depositing wide variety of materials on substrates of different shapes and types.
  • deposition takes place by means of solid particles impacting the metallic as well as non-metallic substrates at very high velocities that is accomplished via a supersonic jet of process/ carrier gas such as air or nitrogen or helium.
  • process/ carrier gas such as air or nitrogen or helium.
  • This method is free from majority of disadvantages common to other metal deposition methods.
  • This method also possesses a number of additional technological, economic, and ecological advantages such as reduced thermal energy input, ability to deposit free forms and options of portability, using clean air or nitrogen or helium as process gas unlike other combustible gases. This makes this method unique and more attractive for depositing wide spectrum of material on substrates.
  • Coatings are applied on substrate requiring a shiny or glossy appearance and protection from sunlight, corrosion and oxidation.
  • Metallic or non- metallic coatings can be applied by using a spray, electrochemically, chemically or mechanically. These coatings modify the surface of the component and increase its lifetime in service.
  • One of such coating technology is thermal spraying. In this family of techniques, coatings are obtained by spraying material in a molten or semi-molten condition.
  • the starting feedstock coating material may be in the form of powder, rod, and wire.
  • gas dynamic cold spray according to our invention is a thermal spraying process yielding thick coating owing majorly to the kinetic energy of the powders than the thermal energy.
  • the thermal energy input to the powders in this technique is negligible.
  • Solid metal powders are accelerated to very high velocities on to the surfaces of the substrate to be coated or repaired by a pressurized process/ carrier gas such as air or nitrogen or helium at a pressure in the range of 0.7 to 5 MPa and at gas temperatures ranging from 298 K to 1273 K.
  • a pressurized process/ carrier gas such as air or nitrogen or helium
  • Fukanuma et al intended to deposit materials by having a preheating zone (50 mm- 1000 mm) before the convergent portion of the nozzle.
  • the objective was to preheat the gas-powder mixture and increase the deformability of the powder particles and deposit thicker coatings at higher efficiencies.
  • it also utilizes a separate heater(s) to heat the preheat zone which is 50 mm to 1000 mm long based on several factors such as length of preheat zone, gas type, gas density, raw material chemistry, raw material shape and size, nozzle material type and wall thickness.
  • the main objective of the present invention is to provide an improved gas dynamic cold spray device with an enhanced ability to deposit better coatings of materials such as Ta, Ta Alloys, Nb, Nb Alloys, Ti, Ti Alloys, Ni, Ni-Cr, Ni super alloys, Stainless Steels, Powder Blends, Nano structured Agglomerated powders, High Entropy Alloys, bio glasses, metal matrix composite powders (with ceramic reinforcements) other than the regular materials such as Cu, Cu Alloys, Sn, Sn Alloys, Ag, Ag Alloys, Zn, Zn Alloys at lower input power and gas consumption.
  • the additional list of materials is useful in various engineering and non-engineering applications.
  • Another objective of the invention is to provide a device and a methodology that is capable of depositing phase pure coatings with high electrical and thermal conductivities for application in electrical industry.
  • Another objective of the invention is to provide a device and a methodology that is capable of depositing phase pure coatings with excellent resistance to cavitation corrosion damage.
  • Another objective of the invention is to provide a device and a methodology that is capable of depositing metallic coating on boiler tubes for high temperature electrical conductivity, oxidation resistance and thermal cycling resistance.
  • Another objective of the invention is to provide a device and a methodology that is capable of depositing metallic coating on non-metallic substrates for power electronics applications.
  • Another objective of the invention is to provide a device and a methodology that is capable of depositing metallic/alloy/cermet coatings on electrical bus bars for joining purpose.
  • Another objective of the invention is to provide a device and a methodology capable of depositing corrosion resistant coatings for sacrificial protection/barrier protection and anodic protection.
  • Another objective of the proposed invention is to provide a device and a methodology capable of depositing refractory metals for high temperature applications (oxidation and corrosion resistance), bio-medical applications, superconductivity applications, for sputter target repair, high temperature wear resistant applications.
  • Another objective is to provide a device and a methodology to deposit nanostructured agglomerated powders and blends for high conductivity and wear resistant applications, bulk metallic glasses for erosion corrosion resistant applications, high entropy alloys for high temperature applications and bio-glass for biomedical applications.
  • Another objective of the present invention is to provide a device and a methodology to obtain very thick coatings or free forms or free-standing coatings akin to additive manufacturing.
  • An improved gas dynamic cold spray device that can deposit a wide variety of materials viz., Cu, Cu Alloys, Sn, Sn Alloys, Ag, Ag Alloys, Zn, Zn Alloys, Stainless Steels, Ni, Ni-Cr, other Ni super alloys, Ta, Ta Alloys, Nb, Nb Alloys, Ti, Ti Alloys, Powder Blends, Nano structured Agglomerated powders, High Entropy Alloys, Bulk Metallic Glasses, bio glass, metal matrix composite powders (with ceramic reinforcements) for a wide range of applications at lower overall power and gas consumption.
  • the process and carrier gas used for all the above is compressed air. Other gases like helium and nitrogen can also be used if the application demands.
  • the device can deposit metallic powder on non-metallic objects as well.
  • Very thick free standing coatings or free forms of one or many of the above mentioned materials can also be accomplished by the present invention.
  • This improved version also includes improved air tight gun design, improved nozzle designs (and nozzle material), improved powder delivery system with an option of depositing material at different deposition rates without compromising the deposition efficiency.
  • Improved design of the device also permits coating deposition on non - flat objects, inaccessible areas useful in real application.
  • the process control side is also equipped with automatic temperature controller, powder feeding by making use of the state of the art electronics.
  • the device is portable and can be carried to outdoor sites for onsite application of coatings.
  • an improved gas dynamic cold spray device system for coating materials to be deposited on the substrates comprising of three major components viz. a) a control panel (1 ), b) a spray gun (2) and c) a powder feeder (3).
  • the control panel (1 ) is an automated one provided with automatic heating and powder feed controls using PLC control panel. It is connected to i) a pneumatic flexible hose (5) for providing compressed carrier/ process gas supply (4); ii) other pneumatic flexible hoses (6 and 7) are connected to the spray gun (2) and powder feeder (3) respectively; iii) electric cable (12, 13, and 8) for powering gas heater (1 1 ), powder feeder (3); and thermocouple (14) of the spray gun (2) respectively.
  • the spray gun (2) houses a nozzle (9) which is of converging and diverging type by virtue of which supersonic velocities are realized. It is connected to i) pneumatic flexible hoses (6) coming from the control panel (1 ); ii) powder feeding tube (15) to which pneumatic flexible hose (7a) carrying powder and carrier gas coming from the powder feeder (3) is merged; iii) thermocouple (14) that is electrically connected to the control panel (1 ) by means of electric cable (8) and iv) gas heater (1 1 ) of the spray gun (2) to which electric cable (12) coming from the control panel (1 ) is connected; and
  • the powder feeder (3) is connected to i) control panel (1 ) by means of pneumatic flexible hose (7) that carries the carrier gas from the control panel (1 ); ii) pneumatic flexible hose (7a) containing carrier gas and powder which merges with powder feeding tube (15) of the spray gun (2); iii) the electric cable (13), connected to the control panel (1 ); and iv) a variable speed motor with light weight "motor-gear box assembly” drives a rotating drum which is a shaft with conical grooves on the surface that delivers the powder.
  • Figure 1 Schematic of the system in block diagram
  • Figure 2 Sketch of the improved spray gun
  • Figure 3 Sketch of the improved nozzle-1
  • an improved gas dynamic cold spray device a system and method of coating on substrates by depositing with wide variety of materials viz., Cu, Cu Alloys, Sn, Sn Alloys, Ag, Ag Alloys, Zn, Zn Alloys, Stainless Steels, Ni, Ni-Cr, other Ni super alloys, Ta, Ta Alloys, Nb, Nb Alloys, Ti, Ti Alloys, Powder Blends, Nano structured Agglomerated powders, High Entropy Alloys, bio glass, metal matrix composite powders (with ceramic reinforcements) for a wide range of applications at an overall lower power and gas consumption by choosing the appropriate combination of nozzle dimensions.
  • materials viz., Cu, Cu Alloys, Sn, Sn Alloys, Ag, Ag Alloys, Zn, Zn Alloys, Stainless Steels, Ni, Ni-Cr, other Ni super alloys, Ta, Ta Alloys, Nb, Nb Alloys, Ti, Ti Alloy
  • the system has three major components. They are the control panel (1 ), spray gun (2) and the Powder feeder (3).
  • the automated control panel (1 ) with automatic heating and powder feed controls is using PLC control panel. Further, the control panel is portable and built to withstand usual loads on the shop floor or onsite.
  • the control panel is connected to the incoming compressed carrier gas (4) selected from air, Nitrogen or Helium, preferably air supply through the pneumatic flexible hose (5) through which process/ carrier gas enters the control panel. Further two more pneumatic flexible hoses (6,7) are also connected to the control panel (1 ). Out of which one pneumatic flexible hose (6) is connected to the improved spray gun (2) for feeding the process to the spray gun (2). The other pneumatic flexible hose (7) connected to the improved powder feeder (3) is used for supplying carrier gas from the control panel (1 ) to the powder feeder (3). Then the pneumatic flexible hose (7a) which carries carrier gas and the powder that is coming out of the powder feeder (3) is connected to the spray gun (2) after merging with the feeder tube (15) near to the process gas entry coming through the pneumatic flexible tube (6).
  • the pneumatic flexible hose (7a) which carries carrier gas and the powder that is coming out of the powder feeder (3) is connected to the spray gun (2) after merging with the feeder tube (15) near to the process gas entry coming through the pneumatic flexible tube
  • the control panel (1 ) is also connected to the improved spray gun (2) by a thermocouple (14) by way of cable (8).
  • the control panel (1 ) is connected to the spray gun electrically by means of cable (12) to power the gas heater (1 1 ) in the spray gun (2).
  • An improved spray gun is shown in Figure 2, which effectively heats the process gas and increases the longevity of heating element by using a copper check nut and seals and/or gaskets (16) and a higher wall thickness (17) at the rear end compared to the front end. This in turn ensures minimal damage to the gun during maintenance and aids in efficient sealing of the gun in addition to increasing the efficiency of heat transfer and increased life of spray gun by minimizing wear of gun inner walls by way of their sacrificial nature.
  • seals are made of flouro polymer based materials such as but not limited to Teflon and Viton.
  • This feature is critical because the spray gun (2) houses the gas heater (1 1 ). Additionally, the spray gun housing can accommodate heaters with varying wattage without changing the basic design. This will further result in capability to reach increased gas preheat temperatures thereby resulting in higher gas velocities and in turn resulting in higher particle velocities and thereby resulting in wider deposition spectrum and better coating quality.
  • the spray gun is portable and light weight and robust. This further helps during the operation, handling and maintenance.
  • the spray gun is also provided with an optional switch (10) to control power supply to the powder feeder (3) especially while it is being operated manually. This makes the device portable and capable of depositing all the materials mentioned in the present invention at lower overall power and gas consumption on site.
  • the spray gun (2) further is connected to pneumatic hoses (6, 7), Powder feeding tube (15), thermocouple (14) and improved nozzle(s) (9).
  • the control panel (1 ) automatically controls current input to the gas heater (1 1 ) within the improved spray gun (2) based on the temperature desired as soon as the gas pressure reaches beyond a set initial pressure. In the case of fall in gas pressure to a value lower than set initial pressure the control panel shuts off current supply to heater to avoid damage to the heater.
  • the powder feeder (3) is shown in Figure 1 . It consists of a variable speed motor with light weight "motor-gear box assembly” that drives a rotating drum which is a shaft with conical grooves on the surface. The dimensions of these grooves are modified to accommodate more powder and deliver efficiently. Powder feeder (3) also has an improved lightweight and efficient "motor-gear box-assembly" enabling upgrading the ratings of the motor-gear box assembly if required.” It can be made of light weight material like aluminium.
  • the control panel (1 ) and powder feeder (3) are connected with pneumatic flexible hose (7) and electrical cable (13). The powder feeder (3) is prompted to be switched ON by the control panel (1 ) as soon as the process gas temperature rises to the desired value fed to the control panel (1 ) by passage of current through the gas heater (1 1 ) provided in the spray gun (2).
  • Process gas line (6) is connected to the spray gun (2) as shown in Figure 2.
  • the spray gun (2) also houses a nozzle (9) by virtue of which supersonic velocities are realized.
  • the basic design of the nozzle is converging diverging type. The sketches of two nozzles are shown in Figure 3 and 4.
  • the nozzles have a converging portion (20,25), a throat portion (22,27) and diverging portion (21 ,26) and inner (19, 24) and outer walls (18, 23).
  • Improved nozzle in Figure 3 in the present invention is capable of depositing coatings at (i) varying deposition rates (50-500 ⁇ /s) (ii) varying spot width or diameter (0.9- 4 mm) (iii) varying spot length or diameter (0.9-12 mm) without compromising the deposition efficiency of the process and without use of any mask or stencil or any additional flow regulators inside the nozzle. Areas requiring thick coatings as in repair applications and areas requiring controlled deposition rates as in electrical and electronic applications can be deposited with equal ease. Improved nozzles in the present invention are power efficient as they dictate the flow and the power requirements to achieve the desired process parameters and hence for different deposition rates and deposition area similar coatings can be obtained at optimal power and gas consumption.
  • the present invention enables successful deposition of materials that have a strong temperature dependence of critical velocity and/or flow stress (Ni, Ni-Cr,IN625 and Cu etc.,) and obviate the need for powder preheater(s) and/or higher gas pressures and gas preheat temperature or monatomic gases such as helium.
  • This is achieved by extending the length of the convergent portion (cylindrical extension if required) with respect to the diverging portion of the nozzle. It can be seen that length of the convergent portion is different for the nozzle given in the Figure 3 and Figure 4.The divergent portion length also can be varied if required.
  • a powder preheater can be used with the current device, if required.
  • the present invention also includes a gas-powder mixing chamber before the converging portion of the nozzle. Additionally, by changing the location of powder injection along the nozzle, particle velocity, particle temperature, particle spread can be controlled to yield the best coatings at optimal power and air consumption.
  • the current invention can utilize one or more or all of the above modifications depending on the application requirements.
  • Highly electrically conductive coatings of silver, copper and tin and composites were applied on metal substrates using the improved gas dynamic cold spray device to demonstrate the efficacy of our system of the instant invention.
  • the metal substrates chosen in this experiment were stainless steel and aluminium as examples and nonmetallic substrates such as ceramics (AI2O3 as an example) and polymers or layered composites can also be chosen to deposit the above mentioned coatings with high electrical conductivity.
  • Water atomized silver powder, spherical tin powder, agglomerated nano Cu-1 % AI2O3 in the size range of 10-45 ⁇ was used as the feedstock powder in each case. The powders had purity close to 99.9%.
  • Stainless steel, aluminium, copper and AI 2 O 3 substrates were grit blasted to induce surface roughness to enable coating deposition.
  • Alumina grit in the size cut of 240 ⁇ was employed at a pressure of 2.5 bar to blast stainless steel whereas a pressure of 1 .5 bar was used to blast aluminium and copper substrates.
  • AI2O3 substrates was grit blasted using micro blasting technique with much finer grit size in the range of 50-60 ⁇ . Post grit blasting the substrates were cleaned thoroughly in an ultrasonic cleaner in acetone medium. The substrates were fixed firmly in a vice.
  • the powder feeder (3) was filled with feedstock powder. The standoff distance between nozzle and the substrate surface was fixed at 15 mm.
  • a nozzle (9) with circular inlet, square throat and rectangular exit was employed in this example.
  • Coating process parameters employed were 8 bar, 100°C for tin and 20 bar, 450°C for silver, Cu-AI 2 O 3 .A total of two passes for silver, 4 passes for Cu- AI2O3 and single pass for tin was used to generate coating of desired thickness and conductivity.
  • a coating thickness of around ⁇ 500 ⁇ was obtained in case of silver at a powder feed rate of 34 g/min and a coating thickness of- 100 ⁇ was obtained in case of tin at a feed rate of 12 g/min.
  • the robot raster speed was 10 mm/s for silver coating and 30 mm/s for tin coating.
  • the thickness desired per pass was different and hence the difference in coating built up per pass.
  • the coating thickness developed was 750-800 ⁇ and the feed rate was maintained at 10 g/min and similar standoff distance and robot speeds were used as in case of silver and tin.
  • the copper coating on Alumina AI2O3 was performed at 10 bar 400°C and standoff distance, robot raster speed was maintained similar to silver and tin coatings.
  • the electrical conductivity of close to -75-85% of bulk silver was obtained (i.e., 46-51 MS/m) and nearly 90% of bulk tin (8-8.2 MS/m) in tin coatings was obtained.
  • the silver coating and tin coating are potential candidates in power and electrical industries respectively.
  • the electrical conductivity of nano Cu-AI 2 O 3 coatings was around 28-32 MS/m and hardness was around 1 .9-2.1 GPa which qualifies it as spot welding electrode material by virtue of favorable combination of electrical conductivity and hardness.
  • the copper coating obtained on Alumina exhibited electrical conductivity in the range of 25-35 MS/m and the dense coating finds use in power electronics application as an electrically and thermally conductive coating on insulating ceramics.
  • is flow stress
  • A is yield stress in quasi static tension or compression
  • B is Strain hardening parameter
  • C is strain rate hardening parameter
  • n is strain hardening exponent and m- thermal softening exponent.
  • improved nozzle (9) shown in fig.4. was utilized and coatings were performed as per the parameters given in table.1 . along with the thickness built up.
  • the main process parameters are the gas pressure and gas temperature which will ultimately decide the resultant gas and particle velocity for a given gas, particle combination.
  • careful design and selection of nozzle can result in reducing the overall energy consumption by reducing the overall gas consumption (reduced gas pressure or reduced gas flow rates) and power consumption (necessary to heat the gas to a desired temperature).
  • the product of "P * T" gas pressure and gas temperature
  • the ratio (P * T) prior an / (P * T) pre sent invention will always be greater than "1 ". This substantiates that the present invention utilizes lower energy to deposit the same materials in the similar thickness range.
  • refractory metals viz., tantalum, titanium and niobium are disclosed. All the above metals and their alloys are refractory (high melting point) in nature and find applications in high temperature applications. Highly dense coatings were obtained at a process parameter combination of 2 MPa or 20 bar and 450°C for all the materials using air as the process and process/ carrier gas.
  • the starting feedstock used in all the above powders was in the size range of 10-45 ⁇ . Tantalum powder used was chemically derived, titanium and niobium were crushed powders. The thickness deposited per pass was around 200-300 ⁇ for Ta and Nb whereas it was around 500- 600 ⁇ in case of titanium. The porosity in the coatings was under 0.8% in case of Ta and Nb and around 3-5% in titanium (which is beneficial from the point of view of biomedical applications).
  • Tantalum and niobium can be used for high temperature applications and also to repair sputter targets in PVD industry. Titanium on the other hand has huge potential in biomedical applications and aerospace applications.
  • solid powder materials like Cu, Cu Alloys, Sn, Sn Alloys, Ag, Ag Alloys, Zn, Zn Alloys, Stainless Steels, Ni, Ni-Cr, other Ni super alloys, Ta, Ta Alloys, Nb, Nb Alloys, Ti, Ti Alloys, Powder Blends, Nano structured Agglomerated powders, High Entropy Alloys, Bulk Metallic Glasses, bio glass, metal matrix composite powders can be applied on metallic/ nonmetallic substrates at an overall optimal power and gas consumption by using the appropriate combination of throat and exit area and divergent and convergent length and without the use of any mask or stencil or any other flow regulator(s) inside the nozzle and without the use of powder preheater(s) and without resorting to higher pressures and temperatures.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
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  • Other Surface Treatments For Metallic Materials (AREA)
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Abstract

An improved gas dynamic cold spray device according to our invention can deposit a wide variety of materials on a variety of substrates. It comprises of a control panel (1), which is connected to a spray gun (2) provided with a converging diverging nozzle (9) by virtue of which supersonic velocities are realized causing the deposition of the material at an overall optimal power and gas consumption without use of any powder preaheater, stencils, flow regulators. Compressed gas supply (4) is provided to the control panel by flexible pneumatic hose (5). Pneumatic flexible hose (6,7) carrying the gas connects the control panel, spray gun, and the powder feeder (3). Powder feeder provides powder to the spray gun by means of carrier gas through pneumatic hose (7a) and powder feeding tube (15). The control panel is electrically connected to powder feeder and gas heater (11) by means of electric cables (13,8,12).

Description

FIELD OF INVENTION
The present invention relates to an improved gas dynamic cold spray device, a system and method of coating by depositing wide variety of materials on substrates of different shapes and types. Here deposition takes place by means of solid particles impacting the metallic as well as non-metallic substrates at very high velocities that is accomplished via a supersonic jet of process/ carrier gas such as air or nitrogen or helium. This method is free from majority of disadvantages common to other metal deposition methods. This method also possesses a number of additional technological, economic, and ecological advantages such as reduced thermal energy input, ability to deposit free forms and options of portability, using clean air or nitrogen or helium as process gas unlike other combustible gases. This makes this method unique and more attractive for depositing wide spectrum of material on substrates. BACKGROUND OF THE INVENTION
Coatings are applied on substrate requiring a shiny or glossy appearance and protection from sunlight, corrosion and oxidation. Metallic or non- metallic coatings can be applied by using a spray, electrochemically, chemically or mechanically. These coatings modify the surface of the component and increase its lifetime in service. One of such coating technology is thermal spraying. In this family of techniques, coatings are obtained by spraying material in a molten or semi-molten condition. The starting feedstock coating material may be in the form of powder, rod, and wire. PRIOR ART
However, gas dynamic cold spray according to our invention is a thermal spraying process yielding thick coating owing majorly to the kinetic energy of the powders than the thermal energy. The thermal energy input to the powders in this technique is negligible. Solid metal powders are accelerated to very high velocities on to the surfaces of the substrate to be coated or repaired by a pressurized process/ carrier gas such as air or nitrogen or helium at a pressure in the range of 0.7 to 5 MPa and at gas temperatures ranging from 298 K to 1273 K. During the impact of the powder particles on the substrates they undergo severe plastic deformation and adhere to the surface, ensuring the effective coating.
The existing systems and methodologies adopted by prior art to obtain coatings of some of the materials mentioned in the present invention rely on attaining higher gas velocities or kinetic energies. This can be obtained by two ways 1 ) increasing the design mach number of the nozzle and 2) increase process gas pressure and process gas preheat temperatures for a given nozzle. By doing the above the power consumption, gas consumption, size and weight of the system becomes very high and result in the increase in overall cost and diluting the portability aspect of such a technique. Also, existing systems relay on additional accessories such as a powder preheater (electrical or electromagnetic) other than Gun, Gas Heater, Powder Feeder and nozzle to accomplish the above which will again add to the weight and size of the total system and increase overall cost. In this connection reference is made to the following prior art documents. EP2175050A1 , US200627687, US20070137560, WO05061 1 16A1 , G. Bae et al., Acta Materialia 60 (2012) 3524-3535. One of the prior art, IN198651 , discloses a device that does not claim the deposition spectrum claimed by the present invention especially deposition of refractory materials (Ta,Ti, Nb and their alloys) and especially materials that have a strong temperature sensitivity to flow stress such as Ni, Ni-Cr, Inconel, Cu and Steel to name a few. The present invention is capable of depositing all the above materials.
As per prior art US20070137560, a separate powder preheating device is claimed by virtue of which powders are preheated prior to entry in to the nozzle. The prior art explains how deposition of materials such as Ni, WC- Co can be enhanced by using such preheating devices. However, in addition to the fact that this prior art adds a separate device to the list of accessories, the probability of heating the powders for long enough time to promote grain growth, decarburization, crystallization and oxidation is increased. Another disadvantage is the increase in power consumption in comparison to normal cold spray process. The process described is more warm spray than cold spray. In the present invention, no additional heating set up is required in this invention and materials that have temperature sensitivity to flow stress and critical velocity can be deposited at an overall lower power and gas consumption.
As per one of the prior art, Fukanuma et al (EP2175050A1 ) intended to deposit materials by having a preheating zone (50 mm- 1000 mm) before the convergent portion of the nozzle. The objective was to preheat the gas-powder mixture and increase the deformability of the powder particles and deposit thicker coatings at higher efficiencies. However, it also utilizes a separate heater(s) to heat the preheat zone which is 50 mm to 1000 mm long based on several factors such as length of preheat zone, gas type, gas density, raw material chemistry, raw material shape and size, nozzle material type and wall thickness. All the above factors not only increase the number of accessories/spares but also increases the total energy consumption in the coating process and for longer preheat zones it is akin to having a separate powder preheater. Addressing this issue, no additional heating set up is required in this invention and materials that have temperature sensitivity to flow stress and critical velocity can be deposited at an overall lower power and gas consumption.
Another prior art US7244466, discloses a nozzle design that incorporates biconical flow regulator or concentrator to produce coating of fine dimensions or spot size. The above invention also uses two types of flow regulators to adjust the dimensions of coating obtained thereof. The present invention performs the same at a lower energy input without using complicated flow regulators that call for additional fabrication steps and adds cost to the entire system.
Hence, a state of the art improved gas dynamic cold spray device and method of coating by depositing a wide variety of materials on substrates of different shapes which is devoid of the above drawbacks. We change the configuration of the gas and powder delivery system to tailor the particle velocity, particle temperature and dispersion to cater to various material requirements. We obtain this at lower power and gas consumption and improved deposition efficiency that has resulted in successful deposition of not only the regular materials such as Cu, Cu Alloys, Sn, Sn Alloys, Ag, Ag Alloys, Zn, Zn Alloys but also deposition of difficult to coat materials such as Ta, Ta Alloys, Nb, Nb Alloys, Ti, Ti Alloys, Ni, Ni-Cr, Ni super alloys, Stainless Steels, Powder Blends, Nano structured Agglomerated powders, High Entropy Alloys, bio glasses, metal matrix composite powders (with ceramic reinforcements) at much lower input energy than currently being used by other systems. The details are disclosed in the detailed description of the present invention.
OBJECTIVES OF THE PRESENT INVENTION
The main objective of the present invention is to provide an improved gas dynamic cold spray device with an enhanced ability to deposit better coatings of materials such as Ta, Ta Alloys, Nb, Nb Alloys, Ti, Ti Alloys, Ni, Ni-Cr, Ni super alloys, Stainless Steels, Powder Blends, Nano structured Agglomerated powders, High Entropy Alloys, bio glasses, metal matrix composite powders (with ceramic reinforcements) other than the regular materials such as Cu, Cu Alloys, Sn, Sn Alloys, Ag, Ag Alloys, Zn, Zn Alloys at lower input power and gas consumption. The additional list of materials is useful in various engineering and non-engineering applications. Another objective of the invention is to provide a device and a methodology that is capable of depositing phase pure coatings with high electrical and thermal conductivities for application in electrical industry.
Another objective of the invention is to provide a device and a methodology that is capable of depositing phase pure coatings with excellent resistance to cavitation corrosion damage.
Another objective of the invention is to provide a device and a methodology that is capable of depositing metallic coating on boiler tubes for high temperature electrical conductivity, oxidation resistance and thermal cycling resistance.
Another objective of the invention is to provide a device and a methodology that is capable of depositing metallic coating on non-metallic substrates for power electronics applications.
Another objective of the invention is to provide a device and a methodology that is capable of depositing metallic/alloy/cermet coatings on electrical bus bars for joining purpose.
Another objective of the invention is to provide a device and a methodology capable of depositing corrosion resistant coatings for sacrificial protection/barrier protection and anodic protection. Another objective of the proposed invention is to provide a device and a methodology capable of depositing refractory metals for high temperature applications (oxidation and corrosion resistance), bio-medical applications, superconductivity applications, for sputter target repair, high temperature wear resistant applications. Another objective is to provide a device and a methodology to deposit nanostructured agglomerated powders and blends for high conductivity and wear resistant applications, bulk metallic glasses for erosion corrosion resistant applications, high entropy alloys for high temperature applications and bio-glass for biomedical applications.
Another objective of the present invention is to provide a device and a methodology to obtain very thick coatings or free forms or free-standing coatings akin to additive manufacturing.
All the above objectives are achieved by providing a system as explained in details in the forthcoming paragraphs.
SUMMARY
An improved gas dynamic cold spray device that can deposit a wide variety of materials viz., Cu, Cu Alloys, Sn, Sn Alloys, Ag, Ag Alloys, Zn, Zn Alloys, Stainless Steels, Ni, Ni-Cr, other Ni super alloys, Ta, Ta Alloys, Nb, Nb Alloys, Ti, Ti Alloys, Powder Blends, Nano structured Agglomerated powders, High Entropy Alloys, Bulk Metallic Glasses, bio glass, metal matrix composite powders (with ceramic reinforcements) for a wide range of applications at lower overall power and gas consumption. The process and carrier gas used for all the above is compressed air. Other gases like helium and nitrogen can also be used if the application demands. In addition to depositing metallic powders on metallic objects, the device can deposit metallic powder on non-metallic objects as well. Very thick free standing coatings or free forms of one or many of the above mentioned materials can also be accomplished by the present invention. This improved version also includes improved air tight gun design, improved nozzle designs (and nozzle material), improved powder delivery system with an option of depositing material at different deposition rates without compromising the deposition efficiency. Improved design of the device also permits coating deposition on non - flat objects, inaccessible areas useful in real application. The process control side is also equipped with automatic temperature controller, powder feeding by making use of the state of the art electronics. The device is portable and can be carried to outdoor sites for onsite application of coatings.
According to the invention there is provided an improved gas dynamic cold spray device system for coating materials to be deposited on the substrates comprising of three major components viz. a) a control panel (1 ), b) a spray gun (2) and c) a powder feeder (3).
The control panel (1 ), is an automated one provided with automatic heating and powder feed controls using PLC control panel. It is connected to i) a pneumatic flexible hose (5) for providing compressed carrier/ process gas supply (4); ii) other pneumatic flexible hoses (6 and 7) are connected to the spray gun (2) and powder feeder (3) respectively; iii) electric cable (12, 13, and 8) for powering gas heater (1 1 ), powder feeder (3); and thermocouple (14) of the spray gun (2) respectively.
The spray gun (2) houses a nozzle (9) which is of converging and diverging type by virtue of which supersonic velocities are realized. It is connected to i) pneumatic flexible hoses (6) coming from the control panel (1 ); ii) powder feeding tube (15) to which pneumatic flexible hose (7a) carrying powder and carrier gas coming from the powder feeder (3) is merged; iii) thermocouple (14) that is electrically connected to the control panel (1 ) by means of electric cable (8) and iv) gas heater (1 1 ) of the spray gun (2) to which electric cable (12) coming from the control panel (1 ) is connected; and
The powder feeder (3) is connected to i) control panel (1 ) by means of pneumatic flexible hose (7) that carries the carrier gas from the control panel (1 ); ii) pneumatic flexible hose (7a) containing carrier gas and powder which merges with powder feeding tube (15) of the spray gun (2); iii) the electric cable (13), connected to the control panel (1 ); and iv) a variable speed motor with light weight "motor-gear box assembly" drives a rotating drum which is a shaft with conical grooves on the surface that delivers the powder.
BRIEF DESCRIPTION OF THE DRAWINGS
Other features and advantages of the present invention should become apparent from the following description of the preferred process, and read in conjunction with the accompanying drawings, which illustrate, by way of example, the principles of the invention.
Figure 1 : Schematic of the system in block diagram
Figure 2: Sketch of the improved spray gun Figure 3: Sketch of the improved nozzle-1
Figure 4: Sketch of the improved nozzle-2
DETAILED DESCRIPTION OF THE INVENTION
In accordance with the invention, there is provided an improved gas dynamic cold spray device, a system and method of coating on substrates by depositing with wide variety of materials viz., Cu, Cu Alloys, Sn, Sn Alloys, Ag, Ag Alloys, Zn, Zn Alloys, Stainless Steels, Ni, Ni-Cr, other Ni super alloys, Ta, Ta Alloys, Nb, Nb Alloys, Ti, Ti Alloys, Powder Blends, Nano structured Agglomerated powders, High Entropy Alloys, bio glass, metal matrix composite powders (with ceramic reinforcements) for a wide range of applications at an overall lower power and gas consumption by choosing the appropriate combination of nozzle dimensions. Here deposition takes place by means of solid particles impacting the metallic as well as non-metallic substrates at very high velocities that is accomplished via a supersonic jet of process/ carrier gas and process gas as compressed air. Nitrogen or helium can also be used based on the requirement with the present system. In addition to coating on the substrates it is also used for repairing the damaged parts. Referring to the schematic Figure.1 , the system has three major components. They are the control panel (1 ), spray gun (2) and the Powder feeder (3). The automated control panel (1 ) with automatic heating and powder feed controls is using PLC control panel. Further, the control panel is portable and built to withstand usual loads on the shop floor or onsite. The control panel is connected to the incoming compressed carrier gas (4) selected from air, Nitrogen or Helium, preferably air supply through the pneumatic flexible hose (5) through which process/ carrier gas enters the control panel. Further two more pneumatic flexible hoses (6,7) are also connected to the control panel (1 ). Out of which one pneumatic flexible hose (6) is connected to the improved spray gun (2) for feeding the process to the spray gun (2). The other pneumatic flexible hose (7) connected to the improved powder feeder (3) is used for supplying carrier gas from the control panel (1 ) to the powder feeder (3). Then the pneumatic flexible hose (7a) which carries carrier gas and the powder that is coming out of the powder feeder (3) is connected to the spray gun (2) after merging with the feeder tube (15) near to the process gas entry coming through the pneumatic flexible tube (6).
The control panel (1 ) is also connected to the improved spray gun (2) by a thermocouple (14) by way of cable (8). In addition, the control panel (1 ) is connected to the spray gun electrically by means of cable (12) to power the gas heater (1 1 ) in the spray gun (2). An improved spray gun is shown in Figure 2, which effectively heats the process gas and increases the longevity of heating element by using a copper check nut and seals and/or gaskets (16) and a higher wall thickness (17) at the rear end compared to the front end. This in turn ensures minimal damage to the gun during maintenance and aids in efficient sealing of the gun in addition to increasing the efficiency of heat transfer and increased life of spray gun by minimizing wear of gun inner walls by way of their sacrificial nature. These seals are made of flouro polymer based materials such as but not limited to Teflon and Viton. This feature is critical because the spray gun (2) houses the gas heater (1 1 ). Additionally, the spray gun housing can accommodate heaters with varying wattage without changing the basic design. This will further result in capability to reach increased gas preheat temperatures thereby resulting in higher gas velocities and in turn resulting in higher particle velocities and thereby resulting in wider deposition spectrum and better coating quality. The spray gun is portable and light weight and robust. This further helps during the operation, handling and maintenance. The spray gun is also provided with an optional switch (10) to control power supply to the powder feeder (3) especially while it is being operated manually. This makes the device portable and capable of depositing all the materials mentioned in the present invention at lower overall power and gas consumption on site.
The spray gun (2) further is connected to pneumatic hoses (6, 7), Powder feeding tube (15), thermocouple (14) and improved nozzle(s) (9). The control panel (1 ) automatically controls current input to the gas heater (1 1 ) within the improved spray gun (2) based on the temperature desired as soon as the gas pressure reaches beyond a set initial pressure. In the case of fall in gas pressure to a value lower than set initial pressure the control panel shuts off current supply to heater to avoid damage to the heater.
The powder feeder (3) is shown in Figure 1 . It consists of a variable speed motor with light weight "motor-gear box assembly" that drives a rotating drum which is a shaft with conical grooves on the surface. The dimensions of these grooves are modified to accommodate more powder and deliver efficiently. Powder feeder (3) also has an improved lightweight and efficient "motor-gear box-assembly" enabling upgrading the ratings of the motor-gear box assembly if required." It can be made of light weight material like aluminium. The control panel (1 ) and powder feeder (3) are connected with pneumatic flexible hose (7) and electrical cable (13). The powder feeder (3) is prompted to be switched ON by the control panel (1 ) as soon as the process gas temperature rises to the desired value fed to the control panel (1 ) by passage of current through the gas heater (1 1 ) provided in the spray gun (2).
The pneumatic hose carrying powder and carrier/ process gas (7a) from the powder feeder (3) merges with powder feeding tube (15) prior to entering in the spray gun (2). Process gas line (6) is connected to the spray gun (2) as shown in Figure 2. The spray gun (2) also houses a nozzle (9) by virtue of which supersonic velocities are realized. The basic design of the nozzle is converging diverging type. The sketches of two nozzles are shown in Figure 3 and 4. The nozzles have a converging portion (20,25), a throat portion (22,27) and diverging portion (21 ,26) and inner (19, 24) and outer walls (18, 23). Improved nozzle in Figure 3 in the present invention is capable of depositing coatings at (i) varying deposition rates (50-500 μιτι/s) (ii) varying spot width or diameter (0.9- 4 mm) (iii) varying spot length or diameter (0.9-12 mm) without compromising the deposition efficiency of the process and without use of any mask or stencil or any additional flow regulators inside the nozzle. Areas requiring thick coatings as in repair applications and areas requiring controlled deposition rates as in electrical and electronic applications can be deposited with equal ease. Improved nozzles in the present invention are power efficient as they dictate the flow and the power requirements to achieve the desired process parameters and hence for different deposition rates and deposition area similar coatings can be obtained at optimal power and gas consumption. This is achieved by reducing or increasing the throat (0.2 mm2 to 16 mm2) and exit areas (0.6 mm2 to 50 mm2) by maintaining a constant exit to throat area ratio or constant mach number or varying them. The mach number can be selected from 2 to 3.5, if required. Based on the actual requirement the throat and exit areas are tailored to yield the best coatings at the optimal power and gas consumption. Another example of the improved nozzle is shown in Figure 4. The present invention enables successful deposition of materials that have a strong temperature dependence of critical velocity and/or flow stress (Ni, Ni-Cr,IN625 and Cu etc.,) and obviate the need for powder preheater(s) and/or higher gas pressures and gas preheat temperature or monatomic gases such as helium. This is achieved by extending the length of the convergent portion (cylindrical extension if required) with respect to the diverging portion of the nozzle. It can be seen that length of the convergent portion is different for the nozzle given in the Figure 3 and Figure 4.The divergent portion length also can be varied if required. While the current device deposits these materials without powder preheating, a powder preheater can be used with the current device, if required. The present invention also includes a gas-powder mixing chamber before the converging portion of the nozzle. Additionally, by changing the location of powder injection along the nozzle, particle velocity, particle temperature, particle spread can be controlled to yield the best coatings at optimal power and air consumption. The current invention can utilize one or more or all of the above modifications depending on the application requirements.
EXAMPLE 1
Deposition of highly electrically conductive coatings
Highly electrically conductive coatings of silver, copper and tin and composites (CU-AI2O3 or Cu-ZrO2 or Cu-SiC) were applied on metal substrates using the improved gas dynamic cold spray device to demonstrate the efficacy of our system of the instant invention. The metal substrates chosen in this experiment were stainless steel and aluminium as examples and nonmetallic substrates such as ceramics (AI2O3 as an example) and polymers or layered composites can also be chosen to deposit the above mentioned coatings with high electrical conductivity. Water atomized silver powder, spherical tin powder, agglomerated nano Cu-1 % AI2O3 in the size range of 10-45 μιη was used as the feedstock powder in each case. The powders had purity close to 99.9%. Stainless steel, aluminium, copper and AI2O3 substrates were grit blasted to induce surface roughness to enable coating deposition. Alumina grit in the size cut of 240 μιη was employed at a pressure of 2.5 bar to blast stainless steel whereas a pressure of 1 .5 bar was used to blast aluminium and copper substrates. AI2O3 substrates was grit blasted using micro blasting technique with much finer grit size in the range of 50-60 μιη. Post grit blasting the substrates were cleaned thoroughly in an ultrasonic cleaner in acetone medium. The substrates were fixed firmly in a vice. The powder feeder (3) was filled with feedstock powder. The standoff distance between nozzle and the substrate surface was fixed at 15 mm. A nozzle (9) with circular inlet, square throat and rectangular exit was employed in this example. Coating process parameters employed were 8 bar, 100°C for tin and 20 bar, 450°C for silver, Cu-AI2O3.A total of two passes for silver, 4 passes for Cu- AI2O3 and single pass for tin was used to generate coating of desired thickness and conductivity. A coating thickness of around ~ 500 μιη was obtained in case of silver at a powder feed rate of 34 g/min and a coating thickness of- 100 μιη was obtained in case of tin at a feed rate of 12 g/min. The robot raster speed was 10 mm/s for silver coating and 30 mm/s for tin coating. Since both the coatings were meant for different applications the thickness desired per pass was different and hence the difference in coating built up per pass. In case of Cu- AI2O3 the coating thickness developed was 750-800 μιη and the feed rate was maintained at 10 g/min and similar standoff distance and robot speeds were used as in case of silver and tin. The copper coating on Alumina AI2O3 was performed at 10 bar 400°C and standoff distance, robot raster speed was maintained similar to silver and tin coatings. The electrical conductivity of close to -75-85% of bulk silver was obtained (i.e., 46-51 MS/m) and nearly 90% of bulk tin (8-8.2 MS/m) in tin coatings was obtained. The silver coating and tin coating are potential candidates in power and electrical industries respectively. The electrical conductivity of nano Cu-AI2O3 coatings was around 28-32 MS/m and hardness was around 1 .9-2.1 GPa which qualifies it as spot welding electrode material by virtue of favorable combination of electrical conductivity and hardness.
The copper coating obtained on Alumina exhibited electrical conductivity in the range of 25-35 MS/m and the dense coating finds use in power electronics application as an electrically and thermally conductive coating on insulating ceramics.
The electrical conductivity was measured using an eddy current probe (FOERSTER, USA). EXAMPLE 2
Development of coatings of materials with high temperature
sensitivity to flow stress and critical velocity
Under cold spray conditions, coating deposition takes place based on the critical velocity of the powder being sprayed. Beyond the critical velocity, at localized interfacial zones, the material strength breaks down and there is a drastic jump in strain and localized temperature leading to bonding between particles and substrate. The governing constitutive equation called Johnson-Cook lasticity model is written as follows where
Figure imgf000016_0002
Figure imgf000016_0001
STRAIN AND STRAIN RATE TEMPERATURE
Where σ is flow stress, A is yield stress in quasi static tension or compression, B is Strain hardening parameter, C is strain rate hardening parameter, n is strain hardening exponent and m- thermal softening exponent.
TABLE-1
Figure imgf000017_0001
value of copper - 1 .09
value of Nickel - 1 .44
value of IN625 - 1 .90
Utilizing the concept above, improved nozzle (9) shown in fig.4. was utilized and coatings were performed as per the parameters given in table.1 . along with the thickness built up.
In cold spray, the main process parameters are the gas pressure and gas temperature which will ultimately decide the resultant gas and particle velocity for a given gas, particle combination. However, careful design and selection of nozzle can result in reducing the overall energy consumption by reducing the overall gas consumption (reduced gas pressure or reduced gas flow rates) and power consumption (necessary to heat the gas to a desired temperature). In the present example, in comparison to the prior art, the product of "P*T" (gas pressure and gas temperature) is much lower to obtain the similar range of coating thicknesses. If the product of P and T in the present case is assumed as "1 ", the ratio (P*T)prior an / (P*T) present invention will always be greater than "1 ". This substantiates that the present invention utilizes lower energy to deposit the same materials in the similar thickness range.
EXAMPLE 3 Development of refractory metal coatings
In the present example, development of coatings of refractory metals viz., tantalum, titanium and niobium are disclosed. All the above metals and their alloys are refractory (high melting point) in nature and find applications in high temperature applications. Highly dense coatings were obtained at a process parameter combination of 2 MPa or 20 bar and 450°C for all the materials using air as the process and process/ carrier gas. The starting feedstock used in all the above powders was in the size range of 10-45 μιη. Tantalum powder used was chemically derived, titanium and niobium were crushed powders. The thickness deposited per pass was around 200-300 μιη for Ta and Nb whereas it was around 500- 600 μιη in case of titanium. The porosity in the coatings was under 0.8% in case of Ta and Nb and around 3-5% in titanium (which is beneficial from the point of view of biomedical applications).
Tantalum and niobium can be used for high temperature applications and also to repair sputter targets in PVD industry. Titanium on the other hand has huge potential in biomedical applications and aerospace applications. Conclusion:
Similarly, we can deposit solid powder materials like Cu, Cu Alloys, Sn, Sn Alloys, Ag, Ag Alloys, Zn, Zn Alloys, Stainless Steels, Ni, Ni-Cr, other Ni super alloys, Ta, Ta Alloys, Nb, Nb Alloys, Ti, Ti Alloys, Powder Blends, Nano structured Agglomerated powders, High Entropy Alloys, Bulk Metallic Glasses, bio glass, metal matrix composite powders can be applied on metallic/ nonmetallic substrates at an overall optimal power and gas consumption by using the appropriate combination of throat and exit area and divergent and convergent length and without the use of any mask or stencil or any other flow regulator(s) inside the nozzle and without the use of powder preheater(s) and without resorting to higher pressures and temperatures.
We have brought out the novel features of the invention by explaining some of the preferred embodiments under the invention, enabling those skilled in the art to understand and visualize our invention. It is also to be understood that the invention is not limited in its application to the details set forth in the above description. Although the invention has been described in considerable detail with reference to certain preferred embodiments thereof, various modifications can be made without departing from the spirit and scope of the invention as described herein above and as defined in the following claims.

Claims

We claim,
1 . An improved gas dynamic cold spray device system for coating materials to be deposited on the substrates comprising of: a control panel (1 ), a spray gun (2) and a powder feeder (3) characterized in that it is comprising of:
a) a control panel (1 ), an automated one provided with automatic heating and powder feed controls using PLC control panel is connected to i) a pneumatic flexible hose (5) for providing compressed carrier/ process gas supply (4); ii) other pneumatic flexible hoses (6 and 7) connected to the spray gun (2) and powder feeder (3) respectively; and iii) electric cable (12, 13, and 8) for powering gas heater (1 1 ), powder feeder (3); and thermocouple (14) of the spray gun (2) respectively;
b) a spray gun (2) housing a nozzle (9) which is of converging diverging type by virtue of which supersonic velocities are realized and connected to i) pneumatic flexible hose (6) coming from the control panel (1 ); ii) powder feeding tube (15) to which pneumatic flexible hose (7a) carrying powder and carrier gas coming from the powder feeder (3) is merged; iii) thermocouple (14) that is electrically connected to the control panel (1 ) by means of electric cable (8) and iv) gas heater (1 1 ) of the spray gun (2) to which electric cable (12) coming from the control panel (1 ) is connected; and
c) powder feeder (3) is connected to i) control panel (1 ) by means of pneumatic flexible hose (7) that carries the carrier gas from the control panel (1 ); ii) pneumatic flexible hose (7a) containing carrier gas and powder which merges with powder feeding tube (15) of the spray gun (2); iii) the electric cable (13), connected to the control panel (1 ); and iv) a variable speed motor with light weight "motor- gear box assembly" that drives a rotating drum which is a shaft with conical grooves on the surface that delivers the powder.
2. The improved gas dynamic cold spray device system as claimed in claim 1 , wherein the control panel (1 ) automatically controls current input to the gas heater (1 1 ) provided inside the spray gun (2) based on the inlet temperature desired as soon as the gas inlet pressure reaches a set initial pressure and in the case of fall in gas pressure to a value lower than set initial pressure, the control panel shuts off current supply to heater to avoid damage to the gas heater.
3. The improved gas dynamic cold spray device system as claimed in claim 1 , wherein the nozzle (9) is provided with a converging portion (20,25), a throat portion (22,27) and diverging portion (21 ,26) and inner (19, 24) and outer walls (18, 23) and is capable of depositing coatings at (i) varying deposition rates (50-500 μιτι/s); (ii) varying spot width or diameter (0.9- 4 mm) and (iii) varying spot length or diameter (0.9-12 mm) without compromising the deposition efficiency of the process at an overall optimal power and gas consumption by using the appropriate combination of throat and exit area and divergent and convergent length for a given application.
4. The improved gas dynamic cold spray device system as claimed in claim 1 , wherein the cross section of the nozzle is selected from circular, rectangular, square or a combination for the inlet, throat and exit to optimize the deposition efficiency for a given throat size or shape by minimizing the boundary layer effects.
5. The improved gas dynamic cold spray device system as claimed in claim 1 , wherein dimension of the nozzle (9) is altered by reducing or increasing the throat area ranging from 0.2 mm2 to 16 mm2 and exit areas ranging from 0.6 mm2 to 50 mm2 by maintaining a constant exit to throat area ratio or constant Mach number selected from 2 to 3.5 to cater to a desired application or deposition rate so as to obtain coatings with fine spot size or lower dimension of coating in the range of 0.9 mm wide or less and/or 3-10 mm long without compromising deposition efficiency and without the use of any stencil or mask or flow regulator(s) resulting in desired deposition rates and deposition area at optimal power and gas consumption.
The improved gas dynamic cold spray device system as claimed in claim 1 , wherein the materials selected from Ni, Ni-Cr, other Ni based alloys (IN 625JN 718), Steels (AISI1045, AISI4340, H13), Cu and Cu alloys(cartridge brass) having a strong temperature dependence of critical velocity and/or flow stress or oxidation sensitive materials selected from Ti, Ti, Ta, Ta alloys, Nb and Nb alloys, Cu and Cu alloys can be successfully deposited without the need of a powder preheater(s), electrical or electromagnetic, and/or higher gas pressures and gas preheat temperature or monatomic gases and is achieved by a combination of extending the length of the convergent portion from 20- 1000 mm with respect to the diverging portion and appropriate throat area ranging from 0.2 mm2 to 16 mm2 and exit areas ranging from 0.6 mm2 to 50 mm2 to achieve the coatings at overall optimal power and gas consumption.
The improved gas dynamic cold spray device system as claimed in claim 1 , wherein the nozzle (9) has a cylindrical extension to the conical convergent portion or conical extension of convergent portion.
The improved gas dynamic cold spray device system as claimed in claim 1 , wherein the process gas is selected from air and/or N2 and/or He and the spray gun (2) heats the process gas to a temperature in the range of 100-700°C at an overall optimal power and gas consumption by using a nozzle with the appropriate combination of throat and exit area and convergent and divergent length for a given application.
The improved gas dynamic cold spray device system as claimed in claim 1 , wherein the spray gun (2) has higher wall thickness (17) at the rear end compared to front end ensuring minimal damage to the gun during maintenance and aids in efficient sealing of the gun because the spray gun (2) houses the gas heater (1 1 ) and the damage to inner walls of the gun is minimized by the use of sacrificial seals made of flouro polymer based materials selected from Teflon or Viton.
10. The improved gas dynamic cold spray device system as claimed in claim 1 , wherein a copper check nut and seals and/or gaskets (16) is provided to the spray gun to increase the longevity of heating element and the spray gun itself in addition to increasing the efficiency of heat transfer and increased life of spray gun by minimizing wear of gun inner walls by way of their sacrificial nature.
1 1 . The improved gas dynamic cold spray device system as claimed in claim 1 , wherein additional heaters with varying wattage ranging from 5 to15 kW so as to develop preheat temperatures froml OO to 700°C are provided in the spray gun (2) thereby resulting in higher gas velocities and in turn resulting in higher particle velocities and ultimately resulting in wider deposition spectrum and better coating quality at an overall optimal power and gas consumption.
12. The improved gas dynamic cold spray device system as claimed in claim 1 , wherein the spray gun as well as the control panel are made portable and suitable for manual operation in shop floor or on site and robust while in operation, handling and maintenance.
13. The improved gas dynamic cold spray device system as claimed in claim 1 , wherein the powder feeder (3) is prompted to be switched ON by the control panel (1 ) as soon as the process gas temperature rises to the desired value fed to the control panel (1 ) by passage of current through the gas heater in spray gun (2).
14. The improved gas dynamic cold spray device system as claimed in claim 1 , wherein the spray gun is also provided with an optional switch (10) to control power supply to the powder feeder (3) especially while it is being operated manually, so as to make the device portable capable of depositing the materials.
15. The improved gas dynamic cold spray device system as claimed in claim 1 , wherein depositing materials for coating on substrates of different shapes is selected from Cu, Cu Alloys, Sn, Sn Alloys, Ag, Ag Alloys, Zn, Zn Alloys, Stainless Steels, Ni, Ni-Cr, Ni based super alloys, Ta, Ta Alloys, Nb, Nb Alloys, Ti, Ti Alloys, Powder Blends, Nano structured Agglomerated powders, High Entropy Alloys, bio glass, metal matrix composite powders with ceramic reinforcements.
16. The improved gas dynamic cold spray device system as claimed in claim 1 , wherein the shape of coating material to be deposited on the substrates is selected from spherical, angular, dendritic, irregular shapes which are processed via different routes selected from gas atomization, water atomization, electrolysis, sintered and crushed, blended or agglomerated.
17. The improved gas dynamic cold spray device system as claimed in claim 1 , wherein the powder material used for coating on the substrates range from 5 to 50 μιη and can have different size distributions within 5-50 μιη.
18 The improved gas dynamic cold spray device system as claimed in claim 1 , wherein it is capable of a) depositing metallic/alloy/cermet coatings on electrical bus bars for joining purpose; b) depositing corrosion resistant coatings for sacrificial protection/barrier protection and anodic protection; and c) depositing refractory metals for high temperature applications (oxidation and corrosion resistance), biomedical applications, superconductivity applications, for sputter target repair, high temperature wear resistant applications, and also used for repairing the damaged parts.
19. The improved gas dynamic cold spray device system as claimed in claim 1 , wherein by changing the location of powder injection along the nozzle, particle velocity, particle temperature, particle spread can be controlled to yield the best coatings at optimal power and gas consumption.
PCT/IN2018/050089 2017-02-26 2018-02-21 An improved gas dynamic cold spray device and method of coating a substrate WO2018154599A1 (en)

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