[go: up one dir, main page]

WO2015006439A1 - Liaison de phase liquide transitoire de revêtements de surface et matériaux couverts de métal - Google Patents

Liaison de phase liquide transitoire de revêtements de surface et matériaux couverts de métal Download PDF

Info

Publication number
WO2015006439A1
WO2015006439A1 PCT/US2014/045936 US2014045936W WO2015006439A1 WO 2015006439 A1 WO2015006439 A1 WO 2015006439A1 US 2014045936 W US2014045936 W US 2014045936W WO 2015006439 A1 WO2015006439 A1 WO 2015006439A1
Authority
WO
WIPO (PCT)
Prior art keywords
metallic
coating
substrate
metal
interlayer
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.)
Ceased
Application number
PCT/US2014/045936
Other languages
English (en)
Inventor
Grant O. COOK
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.)
RTX Corp
Original Assignee
United Technologies Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by United Technologies Corp filed Critical United Technologies Corp
Priority to EP14823037.8A priority Critical patent/EP3019300B1/fr
Priority to EP23208763.5A priority patent/EP4371692A1/fr
Priority to US14/903,844 priority patent/US10933489B2/en
Publication of WO2015006439A1 publication Critical patent/WO2015006439A1/fr
Anticipated expiration legal-status Critical
Priority to US17/185,372 priority patent/US11897051B2/en
Priority to US18/543,257 priority patent/US20240116132A1/en
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
    • B23K20/02—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating by means of a press ; Diffusion bonding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2101/00—Articles made by soldering, welding or cutting
    • B23K2101/34—Coated articles, e.g. plated or painted; Surface treated articles

Definitions

  • the present disclosure generally relates to methods for joining metal-coated materials, and to methods for producing customized metallic coatings. More specifically, this disclosure relates to the use of transient liquid phase (TLP) for joining metal-coated materials and for the production of customized metallic coatings on metallic substrates.
  • TLP transient liquid phase
  • plated polymers metal-covered non-metallic materials such as metal- plated polymers and metal-plated composites (collectively referred to herein as "plated polymers") provide for their use in gas turbine engines. Plated polymers can be substituted for gas turbine engine components previously composed of metals, alloys and traditional composites.
  • metallic structures employed in industries such as, but not limited to, aerospace and automotive industries may derive substantial beneficial properties from the application of metallic coatings to their surfaces. Modifications of the exterior surfaces of metallic structures with metallic coatings may occur without altering the interior of the metallic structures.
  • metallic coatings may be selected based on their ability to impart the surfaces of the metallic structure with one or more desired properties such as, but not limited to, enhanced hardness, wear resistance, oxidation resistance, or conductivity.
  • conventional coating application methods such as cold spraying, may provide a metallic interlock between the metallic substrate and the coating, in some cases it may be desirable to form a more robust and thermally stable bond between the metallic substrate and the coating.
  • a method of bonding components can include positioning an interlayer between a first metallic component and a metal-plated non-metallic component at a bond region, heating the bond region to a bonding temperature to produce a liquid at the bond region, and maintaining the bond region at the bonding temperature until the liquid produced at the bond region has solidified to form a bond between the first metallic component and the metal-plated non- metallic component at the bond region.
  • the interlayer can include an element selected from the group consisting of gallium, indium, selenium, tin, bismuth, iodine, polonium, cadmium, and combinations thereof.
  • a further embodiment of the foregoing method can further include homogenizing the bond.
  • a further embodiment of any of the foregoing methods can further include homogenizing the bond at a temperature substantially equivalent to the bonding temperature.
  • a further embodiment of any of the foregoing methods can further include homogenizing the bond at a temperature lower than the bonding temperature.
  • a further embodiment of any of the foregoing methods can further include that the first metallic component is selected from the group consisting of metal-plated polymers and metal-plated composites.
  • a further embodiment of any of the foregoing methods can further include that one of the first metallic component and the metal-plated non-metallic component are selected from the group consisting of ribs, bosses, flanges, channels, clamps, covers, ducts and brackets.
  • a further embodiment of any of the foregoing methods can further include that the interlayer has a thickness between about 0.00127 mm (0.00005 inches) and about 1.27 mm (0.050 inches).
  • a further embodiment of any of the foregoing methods can further include that the interlayer has at least 50% by weight of an element selected from the group consisting of gallium, indium, selenium, tin, bismuth, iodine, polonium, cadmium, and combinations thereof.
  • a further embodiment of any of the foregoing methods can further include an interlayer having a first layer with a first thickness, a second layer adjacent the first layer with a second thickness greater than the first, and a third layer adjacent the second layer on a side generally opposite the first layer.
  • a further embodiment of any of the foregoing methods can further include that the first layer has an element selected from the group consisting of gallium, indium, selenium, tin, bismuth, iodine, polonium, cadmium, and combinations thereof.
  • a further embodiment of any of the foregoing methods can further include that the second layer has an element selected from the group consisting of refractory metals nickel, iron, cobalt, gold, magnesium, silver, copper, antimony, manganese, palladium, strontium, tellurium, ytterbium, aluminum, calcium, europium, gadolinium, germanium, platinum, rhodium, thulium, vanadium, and combinations thereof.
  • a further embodiment of any of the foregoing methods can further include that the third layer has an element selected from the group consisting of gallium, indium, selenium, tin, bismuth, iodine, polonium, cadmium, and combinations thereof.
  • the second thickness is between about 0.00254 mm (0.0001 inches) and about 1.27 mm (0.050 inches).
  • a further embodiment of any of the foregoing methods can further include that the first thickness is between about 0.2% and about 20% of the second thickness.
  • a further embodiment of any of the foregoing methods can further include that the metal-plated non-metallic component is a metal-plated polymer having a polymer component having a polymer selected from the group consisting of polyphenylene sulfides, polyamides, polyvinylchloride (PVC), polystyrene (PS), polyethylene (PE), polypropylene (PP), styrene - acrylonitrile (SAN), polycarbonate (PC), acrylonitrile styrene acrylate (ASA), acrylonitrile butadiene styrene (ABS), ethylene tetrafluoroethylene fluoropolymer (ETFE), high impact polystyrene (HIPS), polyamide (PA), polybutylene terephthalate (PBT), polyetherimide (PEI), perchloroethylene (PCE), polyether sulfone (PES), polyethylene terephthalate (PET), polysulfone (PSU), polyvin
  • a further embodiment of any of the foregoing methods can further include that the metallic layer has an element selected from the group consisting of nickel, cobalt, iron, gold, silver, copper, alloys of nickel, cobalt, iron, gold, silver, and copper, and combinations thereof. [0023] A further embodiment of any of the foregoing methods can further include that the metallic layer has a thickness between about 0.127 mm (0.005 inches) and about 2.54 mm (0.100 inches).
  • a further embodiment of any of the foregoing methods can further include that the polymer component has an average thickness between about 1.27 mm (0.050 inches) and about 12.7 mm (0.500 inches).
  • a further embodiment of any of the foregoing methods can further include that the metal-plated non-metallic component is a metal-plated composite having a composite component with an average thickness between about 1.27 mm (0.050 inches) and about 12.7 mm (0.500 inches) and a metallic layer covering at least a portion of the composite component such that the metallic layer is located at the bond region of the second component,
  • a further embodiment of any of the foregoing methods can further include that the metallic layer has a thickness between about 0.127 mm (0.005 inches) and about 2.54 mm (0.100 inches).
  • a further embodiment of any of the foregoing methods can further include that the metal-plated non-metallic component is a metal-plated composite having a composite component; and a metallic layer covering at least a portion of the composite component such that the metallic layer is located at the bond region of the second component.
  • a bonded component in accordance with another aspect of the present disclosure, can include one of a polymer component or a composite component, a first metal layer covering the polymer component or composite component, a second metal layer, and a solidified layer located between the first and second metal layers that bonds the first metal layer to the second metal layer.
  • the solidified layer can include an element selected from the group consisting of gallium, indium, selenium, tin, bismuth, iodine, polonium, cadmium, and combinations thereof.
  • the bonded component of the preceding paragraph can optionally include, additionally and/or alternatively, any one or more of the following features, configurations and/or additional components:
  • a further embodiment of the foregoing bonded component can further include that the polymer component comprises a polymer selected from the group consisting of polyphenylene sulfides, polyamides, polyvinylchloride (PVC), polystyrene (PS),
  • the polymer component comprises a polymer selected from the group consisting of polyphenylene sulfides, polyamides, polyvinylchloride (PVC), polystyrene (PS),
  • PE polyethylene
  • PP polypropylene
  • SAN polycarbonate
  • PC acrylonitrile styrene acrylate
  • ASA acrylonitrile butadiene styrene
  • ABS ethylene tetrafluoroethylene fluoropolymer
  • HIPS high impact polystyrene
  • PA polyamide
  • PBT polybutylene terephthalate
  • PEI polyetherimide
  • PCE polyether sulfone
  • PET polyethylene terephthalate
  • PSU polysulfone
  • PUR polyurethane
  • PVDF polyvinylidene fluoride
  • PVDF polyether ether ketone
  • PEEK polyetherimide
  • PEI thermoplastic polyimide
  • condensation polyimide condensation polyimide
  • addition polyimide polyether ketone ketone
  • PEKK polysulfone
  • polyphenylsulfide polyester, epoxy
  • a further embodiment of any of the foregoing bonded components can further include that the second metal layer covers a second polymer component or composite component.
  • a further embodiment of any of the foregoing bonded components can further include that the solidified layer further has an element selected from the group consisting of refractory metals, nickel, iron, cobalt, gold, magnesium, silver, copper, antimony, manganese, palladium, strontium, tellurium, ytterbium, aluminum, calcium, europium, gadolinium, germanium, platinum, rhodium, thulium, vanadium, and combinations thereof.
  • a further embodiment of any of the foregoing bonded components can further include that the polymer component or composite component has an average thickness between about 1.27 mm (0.050 inches) and about 12.7 mm (0.500 inches), and wherein the first metal layer has a thickness between about 0.127 mm (0.005 inches) and about 2.54 mm (0.100 inches).
  • a bonded component can include a first polymer or composite component, a first metal layer covering the first polymer or composite component, a second polymer or composite component, a second metal layer covering the second polymer or composite component, and a solidified layer located between the first and second metal layers that bonds the first metal layer to the second metal layer, the solidified layer comprising an element selected from the group consisting of gallium, indium, selenium, tin, bismuth, iodine, polonium, cadmium, and combinations thereof.
  • the bonded component of the preceding paragraph can optionally include, additionally and/or alternatively, any one or more of the following features, configurations and/or additional components:
  • a further embodiment of the foregoing bonded component can further include that the solidified layer further contains an element selected from the group consisting of refractory metals, nickel, iron, cobalt, gold, magnesium, silver, copper, antimony, manganese, palladium, strontium, tellurium, ytterbium, aluminum, calcium, europium, gadolinium, germanium, platinum, rhodium, thulium, vanadium, and combinations thereof.
  • a further embodiment of any of the foregoing bonded components can further include that the first and second polymer or composite components have a material selected from the group consisting of polyphenylene sulfides, polyamides, polyvinylchloride (PVC), polystyrene (PS), polyethylene (PE), polypropylene (PP), styrene-acrylonitrile (SAN), polycarbonate (PC), acrylonitrile styrene acrylate (ASA), acrylonitrile butadiene styrene (ABS), ethylene tetrafluoroethylene fluoropolymer (ETFE), high impact polystyrene (HIPS), polyamide (PA), polybutylene terephthalate (PBT), polyetherimide (PEI), perchloroethylene (PCE), polyether sulfone (PES), polyethylene terephthalate (PET), polysulfone (PSU), polyurethane (PUR), polyvinylidene
  • a method for providing a part having a customized coating may comprise applying a metallic coating on a surface of a metallic substrate to provide a coated substrate, and bonding the metallic coating to the substrate by a transient liquid phase bonding process to provide the part having the customized coating.
  • the customized coating may have a set of properties different than those of the metallic substrate and the metallic coating.
  • the transient liquid phase bonding process may comprise progressively heating the coated substrate to a bonding temperature.
  • progressively heating the coated substrate to the bonding temperature may cause at least a portion of the metallic coating to melt and form a liquid interlayer, the liquid interlayer to expand in thickness and dissolve a portion of a material forming the metallic substrate, and the liquid interlayer to undergo an isothermal
  • the bond between the customized coating and the metallic substrate may have a melting temperature that exceeds the bonding temperature.
  • heating the coated substrate to the first temperature may cause the metallic coating to melt by direct melting.
  • heating the coated substrate to the first temperature may cause a portion of the metallic coating to melt by eutectic melting, and the liquid interlayer may be formed between the metallic substrate and an un-melted portion of the metallic coating.
  • the method may further comprise heating the part past the bonding temperature to increase a fraction of the material forming the metallic substrate in the customized coating.
  • a method for providing a part having a customized coating may comprise: 1) applying a first metallic coating on a surface of a metallic substrate, 2) applying a second metallic coating on the first metallic coating to provide a coated substrate, and 3) bonding the first metallic coating and the second metallic coating to the metallic substrate by a transient liquid phase bonding process to provide the part having the customized coating.
  • the first metallic coating and the second metallic coating may each have a thickness ranging from less than about 0.001 millimeters up to about 0.5 millimeters.
  • the transient liquid phase bonding process may comprise progressively heating the coated substrate to a bonding temperature.
  • progressively heating the coated substrate to the bonding temperature may comprise: 1) heating the coated substrate to a first temperature that is lower than the bonding temperature to cause at least a portion of at least one of the first metallic coating and the second metallic coating to melt and form at least one liquid interlayer, 2) heating the coated substrate past the first temperature to cause the at least one liquid interlayer to expand in thickness, and 3) heating the coated substrate to the bonding temperature to cause the at least one liquid interlayer to undergo an isothermal solidification process.
  • a bond between the customized coating and the metallic substrate may have a melting temperature that exceeds the bonding temperature.
  • heating the coated substrate to the first temperature may cause the first metallic coating to melt by direct melting.
  • heating the coated substrate to the first temperature may cause a portion of the second metallic coating to melt by eutectic melting, and the at least one liquid interlayer may be formed between an un-melted portion of the first metallic coating an un-melted portion of the second metallic coating.
  • the method may further comprise heating the part past the bonding temperature to increase a fraction of a material forming the metallic substrate in the customized coating.
  • a metallic part having a customized metallic coating may be formed by a method comprising applying one or more metallic coatings to a surface of a metallic substrate to provide a coated substrate, and bonding the one or more metallic coatings to the metallic substrate by a transient liquid phase bonding process.
  • the transient liquid phase bonding process may comprise progressively heating the coated substrate to a bonding temperature to cause: 1) at least a portion of the at least one metallic coating to melt and form a liquid interlayer, 2) the liquid interlayer to expand in thickness, and 3) the liquid interlayer to undergo an isothermal solidification process and provide the part with the customized coating.
  • a bond between the customized metallic coating and the metallic substrate may have a melting temperature that exceeds the bonding temperature.
  • FIG. 1 is a schematic showing a plated polymer component and a metal substrate prior to TLP bonding.
  • FIG. 2A is a block diagram showing one embodiment of a TLP bonding method.
  • FIG. 2B is a block diagram showing another embodiment of a TLP bonding method.
  • FIG. 3 is a schematic showing a plated polymer component and a metal substrate prior to PTLP bonding.
  • FIG. 4 is a cross section view of a nosecone and its internal ribbing connected by TLP bonding.
  • FIG. 5 is a cross section view of a tube having a flange joined by TLP bonding and an O-ring channel joined by TLP bonding.
  • FIG. 6 is a schematic representation illustrating a transient liquid phase (TLP) bonding process for forming a bond between a substrate and a coating in accordance with the present disclosure.
  • TLP transient liquid phase
  • FIG. 7 is a schematic representation illustrating the TLP bonding process for forming a bond between the substrate and two coatings in accordance with the present disclosure.
  • FIG. 8 is a block diagram illustrating the steps involved in bonding the substrate to one or more coatings by the TLP bonding process, in accordance with a method of the present disclosure.
  • plated polymer refers to a metal-covered non-metallic material, including, but not limited to, polymers having a metal covering formed by electroplating, electroless plating, electroforming, spray coating, physical vapor deposition, and other metal deposition methods and composite materials having a metal covering formed by electroplating, electroless plating, electroforming, spray coating, physical vapor deposition, and other metal deposition methods.
  • Composite materials include, but are not limited to, carbon- or glass-fiber-reinforced polymers (thermoplastics and thermosets).
  • TLP Transient liquid phase
  • TLP bonding is used to join a plated polymer component with a metal component.
  • TLP bonding allows plated polymer components to be joined with metal components without the use of the aforementioned destructive welding or brazing and without the physical limitations presented by bolts, rivets and other mechanical joining methods.
  • TLP bonding of plated polymer components can also eliminate weak or thin areas in the plating formed as a result of pitting or recesses formed during the plating process.
  • FIG. 1 is a schematic view showing a plated polymer component and a metal substrate prior to TLP bonding.
  • Plated polymer component 10 includes a non-metallic core 12 and metal layer 14.
  • non-metallic core 12 is formed from a thermoplastic and/or thermoset material, forming a polymer component. Suitable
  • thermoplastic and thermoset materials for non-metallic core 12 include, but are not limited to, polyphenylene sulfides, polyamides, polyvinylchloride (PVC), polystyrene (PS),
  • PE polyethylene
  • PP polypropylene
  • SAN polycarbonate
  • PC acrylonitrile styrene acrylate
  • ASA acrylonitrile butadiene styrene
  • ABS ethylene tetrafluoroethylene fluoropolymer
  • HIPS high impact polystyrene
  • PA polyamide
  • PBT polybutylene terephthalate
  • PEI polyetherimide
  • PCE polyether sulfone
  • PET polyethylene terephthalate
  • PSU polysulfone
  • PUR polyurethane
  • PVDF polyvinylidene fluoride
  • PVDF polyether ether ketone
  • PEEK polyetherimide
  • PEI thermoplastic polyimide
  • condensation polyimide condensation polyimide
  • addition polyimide polyether ketone ketone
  • PEKK polysulfone
  • polyphenylsulfide polyester, epoxy
  • non-metallic core 12 is solid. In other embodiments, non- metallic core 12 is a hollow body. In some embodiments, non-metallic core 12 has an average wall thickness between about 1.27 mm (0.050 inches) and about 12.7 mm (0.500 inches).
  • Non-metallic core 12 can be formed by injection molding, resin transfer molding, vacuum-assisted resin transfer molding, composite layup (autoclave, compression, or liquid molding), compression molding, extrusion, thermoforming, weaving (2D or 3D), braiding, vacuum- forming, machining, laminating, additive manufacturing (liquid bed, powder bed, deposition processes), and other manufacturing techniques.
  • Metal layer 14 is formed over at least a portion of non-metallic core 12 and joined to non-metallic core 12.
  • Metal layer 14 can be formed from any metal having a melting temperature above about 150 °C (302 °F).
  • metal layer 14 contains nickel, cobalt, iron, gold, silver, and copper, alloys of nickel, cobalt, iron, gold, silver, and copper, and combinations thereof.
  • Metal layer 14 can be formed on and joined to non- metallic core 12 by electroplating, electroless plating, electro forming, spray coating, physical vapor deposition, or any other metal deposition method capable of joining metal layer to non- metallic core 12.
  • metallic layer 14 has a thickness between about 0.0254 mm (0.001 inches) and about 2.54 mm (0.100 inches).
  • non-metallic core 12 and metal layer 14 make up plated polymer component 10.
  • Plated polymer component 10 can be any of a number of gas turbine engine components. Suitable components include spinners/nose cones, airfoils, tubes, connectors, covers, ducts, platforms, cases, nacelle components, cascade reversers, brackets, struts, tubes, FADECs, and housings.
  • FIG. 1 also illustrates metal substrate 16.
  • Metal substrate 16 can be formed from any metal having a melting temperature above about 150 °C (302 °F).
  • metal substrate 16 contains nickel, cobalt, iron, gold, silver, and copper, alloys of nickel, cobalt, iron, gold, silver, and copper, and combinations thereof.
  • metal substrate 16 is a structural component to which plated polymer component 10 will be bonded.
  • metal substrate 16 is a rib, boss or flange.
  • Metal substrate 16 can also be a metal -plated polymer component as described above.
  • FIG. 1 further illustrates interlayer 18. As described in greater detail below, interlayer 18 is used to TLP bond plated polymer component 10 to metal substrate 16.
  • Interlayer 18 is located in bond region 20 between metal substrate 16 and metal layer 14 of plated polymer component 10.
  • Interlayer 18 can be composed of a single element, an alloy or a multi-layer combination of elements and/or alloys.
  • interlayer 18 includes elements selected from the group consisting of gallium, indium, selenium, tin, bismuth, iodine, polonium, cadmium, and combinations thereof.
  • interlayer 18 includes other components in addition to the elements listed above. In these cases, interlayer 18 generally includes at least 50% of gallium, indium, selenium, tin, bismuth, iodine, polonium, cadmium, and combinations thereof by weight.
  • interlayer 18 has a thickness between about 0.00127 mm (0.00005 inches) and about 1.27 mm (0.050 inches).
  • FIG. 2A is a block diagram showing the steps of one embodiment of a TLP bonding method for bonding a plated polymer component to a metal substrate.
  • TLP bonding method 30 includes setting up the bond (step 32), heating the bond region to liquefy the interlayer (step 34) and maintaining the bond region at the bonding temperature to allow isothermal solidification of the bond (step 36).
  • step 32 the bond is set up.
  • Polymer component 10 and metal substrate 16 are positioned adjacent one another at bond region 20 as shown in FIG. 1.
  • Interlayer 18 is positioned between metal layer 14 of polymer component 10 and metal substrate 16.
  • interlayer 18 can be positioned at bond region 20 in different ways.
  • interlayer 18 is a thin foil, a powder, a powder compact or a paste.
  • interlayer 18 is typically positioned, spread or brushed on either metal layer 14 or metal substrate 16.
  • interlayer 18 is deposited on either metal layer 14 or metal substrate 16 by physical vapor deposition, sputtering, electroplating, electro forming or applying interlayer 18 as a solution and vaporizing the solvent.
  • metal layer 14 metal layer 14, metal substrate 16 and interlayer 18 are held in place at bond region 20.
  • pressure is applied to bond region 20 to maintain alignment of polymer component 10 and metal substrate 16 and promote bonding.
  • a fixture is used to maintain alignment of polymer component 10 and metal substrate 16 (the bond can be formed with little or no pressure).
  • bond region 20 is heated to liquefy interlayer 18 in step 34.
  • Bond region 20 can be heated using radiation (visible or infrared), conduction, induction, resistance heating or a laser.
  • step 34 (and subsequent steps) can be carried out under vacuum conditions, in an inert atmosphere or ambient atmospheric conditions. Inert atmospheres include, but are not limited to, argon, nitrogen, hydrogen and a mixture of nitrogen and hydrogen.
  • Bond region 20 is heated to a bonding temperature greater than or equal to either (1) the melting temperature of interlayer 18 or (2) the minimum eutectic reaction temperature between interlayer 18 and (a) metal layer 14 or (b) metal substrate 16.
  • the melting temperature of interlayer 18 depends on the particular makeup of interlayer 18.
  • the bonding temperature used in step 34 is substantially equal to the melting temperature (direct or eutectic) of interlayer 18. In other embodiments, the bonding temperature is between about 11.1 °C (20 °F) and about 33.3 °C (60 °F) greater than the melting temperature of interlayer 18. Once the melting point of interlayer 18 is reached, interlayer 18 begins to liquefy. Typically, the bonding temperature is greater than the melting point of interlayer 18 to ensure complete melting of interlayer 18 and to increase the rate at which interlayer 18 diffuses into metal layer 14 and metal substrate 16 at bond region 20.
  • liquefied interlayer 18 dissolves (or "melts back") metal layer 14 and metal substrate 16 at bond region 20.
  • the temperature at bond region 20 is maintained at the bonding temperature to allow isothermal solidification of the bond.
  • interlayer 18 diffuses into metal layer 14 and metal substrate 16 at bond region 20.
  • bond region 20 is kept at the bonding temperature while this diffusion occurs. Because the diffusion occurs isothermally, the liquid region of interlayer 18 contracts to maintain equilibrium and interlayer 18 solidifies with metal layer 14 and metal substrate 16 at bond region 20. Once interlayer 18 has isothermally solidified, the TLP bond is complete.
  • Method 30A includes homogenization step 38 following isothermal solidification step 36. Homogenization increases the melting temperature of the resulting bond formed at bond region 20. Homogenization step 38 includes heating bond region 20. Homogenization can be performed at or near the bonding temperature used in steps 34 and 36 or at a temperature lower than the bonding temperature. Homogenization can be performed immediately after step 36, where bond region 20 is held at an elevated temperature for an extended time. Alternatively, homogenization can be performed at a later time as a post-bonding treatment. After homogenization, the resulting bond formed at bond region 20 between metal layer 14 and metal substrate 16 can have a remelting temperature hundreds of degrees Celsius above the initial melting temperature of interlayer 18.
  • Partial transient liquid phase (PTLP) bonding is a variant of TLP bonding that is typically used to join ceramics. PTLP bonding can also be used to join metal layer 14 and metal substrate 16. PTLP requires an interlayer composed of multiple layers. In some embodiments, PTLP is performed using an interlayer having a relatively thick refractory core sandwiched by thin, lower-melting layers on each side.
  • FIG. 3 is a schematic view showing a plated polymer component and a metal substrate prior to PTLP bonding including interlayer 18A having first layer 18B, second (middle) layer 18C and third layer 18D. FIG. 3 is not drawn to scale in order to show the distinct layers of interlayer 18 A.
  • middle layer 18C of interlayer 18A used in PTLP bonding includes elements selected from the group consisting of refractory metals nickel, iron, cobalt, gold, magnesium, silver, copper, antimony, manganese, palladium, strontium, tellurium, ytterbium, aluminum, calcium, europium, gadolinium, germanium, platinum, rhodium, thulium, vanadium and combinations thereof and has a thickness between about 0.00254 mm (0.0001 inches) and about 1.27 mm (0.050 inches).
  • interlayer 18 includes other components in addition to the elements listed above.
  • interlayer 18 generally includes at least 50% of nickel, iron, cobalt, gold, magnesium, silver, copper, antimony, manganese, palladium, strontium, tellurium, ytterbium, aluminum, calcium, europium, gadolinium, germanium, platinum, rhodium, thulium, vanadium, and combinations thereof by weight.
  • the thinner outer layers (18B and 18D) of interlayer 18 include elements selected from the group consisting of gallium, indium, selenium, tin, bismuth, iodine, polonium, cadmium, and combinations thereof, and have thicknesses between about 0.2% and about 20% of the thickness of middle layer 18C.
  • interlayer 18 includes other components in addition to the elements listed above.
  • interlayer 18 generally includes at least 50%> of gallium, indium, selenium, tin, bismuth, iodine, polonium, cadmium, and combinations thereof by weight.
  • PTLP bonding is performed as described above with respect to TLP bonding. In the case of PTLP bonding, different bonding temperatures can be utilized and the rate at which interlayer 18 A melts and diffuses may differ due to the multi-layer nature of interlayer 18 A.
  • FIG. 4 illustrates one example of TLP or PTLP bonding between a plated polymer component and a metal substrate.
  • FIG. 4 is a cross-section view of a nosecone and its internal ribs.
  • nosecone 40 is a metal-plated polymer component having a polymer or composite core and a metal layer covering the core.
  • nosecone 40 includes outer shell 42.
  • Circular ribs 44 A and 44B and axial ribs 46 are structures that provide support to nosecone 40.
  • one or more of circular ribs 44A and 44B and axial ribs 46 are metal-plated polymers.
  • Bonding interlayer 48 is positioned between outer shell 42 and circular ribs 44A and 44B and axial ribs 46, and can be a single layer or a multi-layer interlayer to produce a TLP or PTLP bond, respectively, as described above.
  • FIG. 4 is not drawn to scale to better illustrate the layers of the cross- section view of nosecone 40.
  • Circular ribs 44 A and 44B and axial ribs 46 are TLP or PTLP bonded to inner surface 50 of nosecone 40 and the external surfaces of ribs 44 A, 44B, and 46 as described above with respect to FIGs. 2A and 2B.
  • one or more of circular ribs 44A and 44B and axial ribs 46 are Ni-based alloys.
  • FIG. 5 illustrates another example of TLP bonding between a plated polymer component and a metal substrate.
  • FIG. 5 is a cross-section view of a tube having a flange joined to the tube by TLP or PTLP bonding and an O-ring channel joined to the tube by TLP or PTLP bonding.
  • Tube 52 is generally cylindrical and includes wall 54 having outer surface 56.
  • tube 52 is a metal-plated polymer component having a polymer or composite core and a metal layer at outer surface 56.
  • outer surface 56 is metallic. Attached to tube 56 along outer surface 56 are flange 58 and O-ring channel 60.
  • Flange 58 and O-ring channel 60 are metal -plated polymer components or have an outer metallic surface and are TLP or PTLP bonded to outer surface 56 of tube 52 as described above with respect to FIGs. 2A and 2B.
  • TLP and PTLP bonding allows the formation of a typical component using easily molded or machined parts. While FIGs. 4 and 5 illustrate just two particular embodiments of metal-plated polymer components or features that are TLP bonded to other structures, many other examples are possible such as ducts, covers, brackets, clamps, bosses, flanges, ribs, and channels.
  • TLP bonding allows plated polymer components to be bonded to metal components without deforming or destroying the polymer core of the plated polymer.
  • TLP bonding provides a strong bond that can be used above the bonding temperature and TLP bonded parts do not possess the disadvantages and limitations of conventional hardware and assembly devices such as bolts and rivets.
  • the first coating 70 may consist of any metallic material and it may be applied by any suitable method apparent to those of ordinary skill in the art. Such methods may include, but are not limited to, chemical vapor deposition, physical vapor deposition, plating, cold spraying, or plasma spraying.
  • the substrate 72 may be any metallic structure, such as, but not limited to, a pure metal, an alloy, an intermetallic, or a metal matrix composite.
  • the first coating 70 may be applied to one or more surfaces of the substrate 72 and it may be capable of imparting the substrate 72 with one or more properties favorable to its operation and use, such as, but not limited to, enhanced hardness, wear resistance, oxidation resistance, thermal conductivity, and/or electrical conductivity.
  • the first coating 70 may have a thickness from less than about one (1) micron (about 0.001 mm) to up to about 500 microns (about 0.5 mm).
  • the coated substrate may be progressively heated (symbolized by ⁇ ) to a bonding temperature (T 2 ) which is selected based on the composition of the first coating 70.
  • T 2 a bonding temperature
  • a liquid interlayer 76 may form at the interface between the coating 70 and the substrate 72 by either direct melting 73 of the first coating 70 or by eutectic melting 75 between the first coating 70 and the substrate 72, as shown in FIG. 6.
  • Direct melting 73 of the first coating 70 may result if the first coating 70 is heated beyond its melting point such that the entire first coating 70 liquefies and forms the interlayer 76.
  • eutectic melting 75 of the first coating 70 may result if the substrate 72 and the first coating 70 form a eutectic product at the interface of the first coating 70 and the substrate 72 and the eutectic product has a melting temperature lower than the melting temperatures of the first coating 70 and the substrate 72.
  • the interlayer 76 formed by eutectic melting 75 may be a thin liquid layer located between the substrate 72 and an un-melted layer of the first coating 70, as shown in FIG. 1.
  • dissolution may occur in which the solid-liquid boundaries of the interlayer 76 may expand and dissolve some of the material of the substrate 72 (and an un-melted layer of the first coating 70, if present), as shown.
  • the interlayer 76 may expand up to several times its original thickness.
  • the liquid interlayer 76 may diffuse into the substrate 72 and undergo an isothermal solidification process 78 until all of the liquid of the interlayer 76 has solidified and a custom coating 82 is formed at the outer surface of the substrate 72.
  • the liquid of the interlayer 76 migrates towards the surface by solidifying at the interface with substrate 72 and liquefying material at the interface with the first coating 70. This process continues until the first coating 70 is completely consumed and solidification of interlayer 76 proceeds as described previously to yield the custom coating 82, as shown. At this stage, the custom coating process may be terminated.
  • the custom coating 82 may compositionally resemble a gradient of the first coating 70 material in the substrate 72 material and may have a smooth transition of grain boundaries and properties between the outer surface and the substrate 72. Alternatively, the custom coating 82 may be diffused in with continued heating to form different gradients having increasing proportions of the substrate 72 with increased heating. In any event, whether the custom coating 82 undergoes homogenization after the TLP bonding process or not, the completion of the TLP bonding process 74 will provide a part 85 having a custom coating 82 with a functionally graded structure having microstructural, mechanical, and physical properties different than those of the substrate 72 and the first coating 70.
  • the custom coating 82 may have properties of an intermetallic material composed of nickel and aluminum.
  • the custom coating 82 may have a melting temperature that exceeds the bonding temperature (T 2 ) used to join the substrate 72 and the first coating 70 and may therefore exhibit enhanced thermal stability.
  • T 2 bonding temperature
  • the bonding of multiple coatings (a first coating 70 and a second coating 90) to the outer surface of the substrate 72 by the TLP bonding process 74 is depicted in FIG. 7.
  • the second coating 90 may be a metallic coating which differs in composition from the first coating 70 and may impart one or more selected properties to the substrate 72 which may differ from the properties provided by the first coating 70.
  • the first coating 70 and the second coating 90 may be deposited sequentially on one or more surfaces of the substrate 72 by any deposition method apparent to those of ordinary skill in the art (e.g., chemical vapor deposition, physical vapor deposition, plating, cold spraying, plasma spraying, etc.).
  • the second coating 90 may also have a thickness from less than about one (1) micron (about 0.001 mm) to up to about 500 microns (about 0.5 mm).
  • the coated substrate may then be progressively heated (symbolized by ⁇ ) to a bonding temperature (T 2 ), as shown. Upon reaching a suitable temperature (Ti) during the heating process, melting of all of the first coating 70 may occur by direct melting 73 to form an interlayer 76 between the second coating 90 and the substrate 72.
  • the eutectic product may melt by eutectic melting 75 to form a thin interlayer 76 between the substrate 72 and the first coating 70 and/or between the first coating 70 and the second coating 90, as shown.
  • the interlayer(s) 76 may expand in thickness by a dissolution/expansion process 77, as explained above. Once the bonding temperature T 2 is reached, the interlayer(s) 76 may diffuse and isothermally solidify into the substrate 72 (and any solid portions of the first coating 70 and second coating 90) to form a custom coating 82 between the substrate 72 and the first coating 70. In this way, a multi-layered custom coating may also be formed of the first coating 70 and the second coating 90 as the liquid interfaces migrate towards the surface, as described above.
  • the custom coating 82 may be a gradient of the composition of the substrate 72 and the first coating 70 and may have microstructural and physical properties between those of the substrate 72 and the first coating 70. Similarly, if a custom coating is formed between the first coating 70 and the second coating 90, it may compositionally resemble a gradient of the first coating 70 and the second coating 90 and have microstructural and physical properties resembling both coatings. Homogenization of the custom coating 82 may be achieved, if desired, with further heating as described above. The resulting part 92 may exhibit any advantageous properties provided by the first coating 70 and/or the second coating 90.
  • multiple coatings may be bonded to one or more surfaces of the substrate 72 and one may select and combine coatings according to desired combinations of physical properties.
  • more than two coatings can be utilized to further enhance the custom coatings that can be produced by TLP bonding in this manner.
  • one or more coatings may be utilized in different sections of the component to produce locally customized coatings.
  • FIG. 8 illustrates steps which may be involved in bonding one or more metallic coatings to one or more exterior surfaces of the substrate 72 by the TLP bonding process 74.
  • one or more coatings (such as the first coating 70) may be applied to one or more surfaces of the substrate 72 by any conventional deposition process selected by a skilled artisan.
  • the coated substrate may then be heated to a first temperature (Ti) which may cause a liquid interlayer 76 to form between the surface of the substrate 72 and the coating by direct or eutectic melting according to a block 96 and a block 98, as shown.
  • interlayer(s) 76 may also be formed between each of the coatings as illustrated in FIG. 7.
  • the coated substrate may be further heated past Ti which causes expansion of the liquid interlayer(s) 76. Further heating of the coated substrate to the bonding temperature (T 2 ) may cause the diffusion and isothermal solidification of the interlayer(s) 76 into the substrate 72 (and adjacent coatings which remain in a solid state) according to a block 102 and a block 104, as shown.
  • T 2 bonding temperature
  • the customized coating 82 may be formed between the substrate 72 and the coating(s), and the customized coating 82 may have microstructural and physical properties between those of the substrate 72 and the coating(s) (block 106).
  • optional continued heating may be employed according to a block 106.
  • the part having a customized coating 82 bonded to the substrate 72 may then be provided according to a block 108, as shown.
  • TLP bonding of one or more metallic coatings to metallic substrates can find applicability in many situations, including, but not limited to, the production of metallic components having specialized or customized coatings.
  • the TLP bonding process forms a strong bond or joint between the metallic substrate and the coating(s) which has microstructural and physical properties between those of the substrate and the coating materials.
  • one may select and combine coatings having varying desirable properties to form specialized coatings by the TLP bonding process.
  • some conventional coating methods for metals e.g., cold spraying
  • TLP bonding may provide a more robust and thermally stable bond between the substrate and coating.
  • the resulting bond between the metallic substrate and the coating may have a melting temperature in excess of the bonding temperature used for TLP bonding, such that the formed bond may operate at temperatures well above the bonding temperature.
  • This feature may be advantageous, for example, when joining temperature-sensitive materials whose micro-structures could be damaged by too much thermal energy input. It is expected that the technology as disclosed herein may find wide industrial applicability for component fabrication in various industries including, but not limited to, aerospace and automotive industries.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un procédé de liaison de composants. Le procédé peut comprendre le positionnement d'une intercouche entre un composant métallique et un composant non métallique plaqué de métal au niveau d'une région de liaison, le chauffage de la région de liaison à une température de liaison pour produire un liquide au niveau de la région de liaison, et le maintien de la région de liaison à la température de liaison jusqu'à ce que le liquide se soit solidifié pour former une liaison entre le composant métallique et le composant non métallique plaqué de métal au niveau de la région de liaison. Un procédé de fourniture d'une partie ayant un revêtement personnalisé est également divulgué. Le procédé peut comprendre l'application d'un revêtement métallique sur une surface d'un substrat métallique, et la liaison du revêtement métallique au substrat métallique par un processus de liaison de phase liquide transitoire pour fournir la partie ayant le revêtement personnalisé.
PCT/US2014/045936 2013-07-09 2014-07-09 Liaison de phase liquide transitoire de revêtements de surface et matériaux couverts de métal Ceased WO2015006439A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP14823037.8A EP3019300B1 (fr) 2013-07-09 2014-07-09 Liaison de phase liquide transitoire de matériaux couverts de métal
EP23208763.5A EP4371692A1 (fr) 2013-07-09 2014-07-09 Liaison en phase liquide transitoire de revêtements de surface et de matériaux recouverts de métal
US14/903,844 US10933489B2 (en) 2013-07-09 2014-07-09 Transient liquid phase bonding of surface coatings metal-covered materials
US17/185,372 US11897051B2 (en) 2013-07-09 2021-02-25 Transient liquid phase bonding of surface coatings and metal-covered materials
US18/543,257 US20240116132A1 (en) 2013-07-09 2023-12-18 Transient liquid phase bonding of surface coatings and metal-covered materials

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201361884118P 2013-07-09 2013-07-09
US201361844032P 2013-07-09 2013-07-09
US61/884,118 2013-07-09
US61/844,032 2013-07-09

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US14/903,844 A-371-Of-International US10933489B2 (en) 2013-07-09 2014-07-09 Transient liquid phase bonding of surface coatings metal-covered materials
US17/185,372 Division US11897051B2 (en) 2013-07-09 2021-02-25 Transient liquid phase bonding of surface coatings and metal-covered materials

Publications (1)

Publication Number Publication Date
WO2015006439A1 true WO2015006439A1 (fr) 2015-01-15

Family

ID=52280565

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2014/045936 Ceased WO2015006439A1 (fr) 2013-07-09 2014-07-09 Liaison de phase liquide transitoire de revêtements de surface et matériaux couverts de métal

Country Status (1)

Country Link
WO (1) WO2015006439A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20230240826A1 (en) * 2022-02-01 2023-08-03 Amadeus Hornemann Procedure for repairing and treating pelvic prolapse in a female patient, a medical instrument for perforation of the cervix, a procedure for removing tendon tissue of a tendon from a human or animal body, and a procedure for the preparation of tendon tissue
US12168713B2 (en) 2020-06-10 2024-12-17 Inkbit, LLC Materials for photoinitiated cationic ring-opening polymerization and uses thereof
CN119175373A (zh) * 2024-11-22 2024-12-24 中国航发沈阳黎明航空发动机有限责任公司 一种适用于镍基合金tlp连接的复合中间层的制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0145785A1 (fr) 1983-05-31 1985-06-26 Hughes Aircraft Co Composants soudables en plastique metallise.
WO1995004627A1 (fr) * 1993-08-10 1995-02-16 The Regents Of The University Of California Liaison de ceramique en phase liquide transitoire
US20030141345A1 (en) 2002-01-25 2003-07-31 Ngk Insulators, Ltd. Bonded member comprising different materials, and production method thereof
US20070152026A1 (en) * 2005-12-30 2007-07-05 Daewoong Suh Transient liquid phase bonding method
US20080035707A1 (en) * 2006-08-14 2008-02-14 The Regents Of The University Of California Transient-liquid-phase joining of ceramics at low temperatures
EP2047937A2 (fr) * 2007-10-10 2009-04-15 Zimmer, Inc. Procédé de liaison d'une structure en tantale à un substrat en alliage de cobalt
US20130143058A1 (en) * 2009-06-02 2013-06-06 Integran Technologies, Inc. Metal-coated polymer article

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0145785A1 (fr) 1983-05-31 1985-06-26 Hughes Aircraft Co Composants soudables en plastique metallise.
WO1995004627A1 (fr) * 1993-08-10 1995-02-16 The Regents Of The University Of California Liaison de ceramique en phase liquide transitoire
US20030141345A1 (en) 2002-01-25 2003-07-31 Ngk Insulators, Ltd. Bonded member comprising different materials, and production method thereof
US20070152026A1 (en) * 2005-12-30 2007-07-05 Daewoong Suh Transient liquid phase bonding method
US20080035707A1 (en) * 2006-08-14 2008-02-14 The Regents Of The University Of California Transient-liquid-phase joining of ceramics at low temperatures
EP2047937A2 (fr) * 2007-10-10 2009-04-15 Zimmer, Inc. Procédé de liaison d'une structure en tantale à un substrat en alliage de cobalt
US20130143058A1 (en) * 2009-06-02 2013-06-06 Integran Technologies, Inc. Metal-coated polymer article

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3019300A4

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12168713B2 (en) 2020-06-10 2024-12-17 Inkbit, LLC Materials for photoinitiated cationic ring-opening polymerization and uses thereof
US20230240826A1 (en) * 2022-02-01 2023-08-03 Amadeus Hornemann Procedure for repairing and treating pelvic prolapse in a female patient, a medical instrument for perforation of the cervix, a procedure for removing tendon tissue of a tendon from a human or animal body, and a procedure for the preparation of tendon tissue
CN119175373A (zh) * 2024-11-22 2024-12-24 中国航发沈阳黎明航空发动机有限责任公司 一种适用于镍基合金tlp连接的复合中间层的制备方法

Similar Documents

Publication Publication Date Title
US20240116132A1 (en) Transient liquid phase bonding of surface coatings and metal-covered materials
KR101054462B1 (ko) 모재의 강도를 초과하는 접합강도를 갖는, 중간층을 이용한강계열 합금과 티타늄 또는 티타늄계열 합금 간의 고강도 이종금속 접합방법
US10752557B2 (en) Method of bonding a metallic component to a non-metallic component using a compliant material
US20160152005A1 (en) Hybrid plated composite stack
WO2015006439A1 (fr) Liaison de phase liquide transitoire de revêtements de surface et matériaux couverts de métal
EP3368240B1 (fr) Procédé de fabrication
EP3083774B1 (fr) Fixation élastique pour composant composite à matrice organique
EP4238753A1 (fr) Stratifiés composites avec des couches métalliques et procédés associés
FR3031274A1 (fr) Structure comportant des lignes electriquement conductrices en surface et procede pour la realisation de lignes electriquement conductrices sur une face d'une structure
EP3003720B1 (fr) Liaison en phase liquide partiellement transitoire et durcie par précipitation
EP4371692A1 (fr) Liaison en phase liquide transitoire de revêtements de surface et de matériaux recouverts de métal
US20150183691A1 (en) Manufacturing method and repairing method
US10071543B2 (en) Precipitation hardened partial transient liquid phase bond
JP2011185280A (ja) ロケット構造体の構成部品の製造方法
CN108349215B (zh) 形成金属复合材料
JP2019122967A (ja) 銅錫合金の製造方法
US20130081873A1 (en) Feed-through assembly
WO2021246278A1 (fr) Article moulé et son procédé de production
JP2006255735A (ja) 部材の接合方法、複合部材の製造方法、接合体および複合部材
JP2016093948A (ja) 熱可塑性プリプレグ成形品の製造方法
TW201703991A (zh) 三維列印方法
JPH03285003A (ja) 多機能材料の製造方法
FR2468460A1 (fr) Procede d'assemblage de pieces metalliques permettant la production d'un materiau plastique arme et produit obtenu
EP3019642A1 (fr) Polymères plaqués renforcés
JP2012187481A (ja) 積層体の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14823037

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 14903844

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2014823037

Country of ref document: EP