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WO2017009295A1 - Aube de turbomachine à structure de protection, turbomachine et procédé de formation d'une structure de protection - Google Patents

Aube de turbomachine à structure de protection, turbomachine et procédé de formation d'une structure de protection Download PDF

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Publication number
WO2017009295A1
WO2017009295A1 PCT/EP2016/066445 EP2016066445W WO2017009295A1 WO 2017009295 A1 WO2017009295 A1 WO 2017009295A1 EP 2016066445 W EP2016066445 W EP 2016066445W WO 2017009295 A1 WO2017009295 A1 WO 2017009295A1
Authority
WO
WIPO (PCT)
Prior art keywords
edging
spraying
protective
leading edge
stripes
Prior art date
Application number
PCT/EP2016/066445
Other languages
English (en)
Inventor
Michelangelo Bellacci
Federico Iozzelli
Gabriele Masi
Leonardo Tognarelli
Original Assignee
Nuovo Pignone Tecnologie Srl
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 Nuovo Pignone Tecnologie Srl filed Critical Nuovo Pignone Tecnologie Srl
Priority to EP16736885.1A priority Critical patent/EP3322832B1/fr
Priority to PL16736885T priority patent/PL3322832T3/pl
Priority to BR112018000669-6A priority patent/BR112018000669B1/pt
Priority to JP2017567771A priority patent/JP6847059B2/ja
Publication of WO2017009295A1 publication Critical patent/WO2017009295A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/01—Selective coating, e.g. pattern coating, without pre-treatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/08—Metallic material containing only metal elements
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18—After-treatment

Definitions

  • Embodiments of the subject matter disclosed herein correspond to turbomachine blades with protective structure, turbomachines (in particular steam turbines), and methods of forming protective structure.
  • the blades of steam turbines are often subject to liquid droplet erosion.
  • Structures for protecting turbomachine blades against erosion, corrosion or wear may consist of layers formed on the surface of the blades or inserts fit in the body of the blades.
  • Protective layers may be formed for example by laser cladding or by cold spraying. Both these technologies are effective.
  • laser cladding heats the blades and may cause for example residual stress in the blades and/or distortion of the blades and may foster "stress corrosion cracking", while cold spraying hits the blades and may cause for example erosion of the edges of the blades during formation of the layers. It is to be noted that laser cladding is more expensive than cold spraying, but is quicker.
  • turbomachine blades there is a general need for improving the protective structures of turbomachine blades and the methods of forming them. This need is particularly high for blades of steam turbines in the fields of "Oil & Gas” (i.e. machines and plants for exploration, production, storage, refinement and distribution of oil and/or gas) and "Energy” (i.e. machines and plants for power generation).
  • First embodiments of the subject matter disclosed herein relate to a turbomachine blade.
  • the turbomachine blade is provided with an airfoil portion having a leading edge and a trailing edge and first and second sides connecting the leading edge and the trailing edge, and with a protective structure comprising a protective edging and first and second protective stripes; the protective edging is located on the leading edge; the first protective stripe is located on the first side and adjacent to the edging; the second protective stripe is located on the second side and adjacent to the edging; the edging is formed by laser cladding or welding or plasma spraying or detonation spraying or wire arc spraying or flame spraying or high velocity oxyfuel coating spraying or warm spraying; the first and second stripes are formed by cold spraying.
  • Second embodiments of the subject matter disclosed herein relate to a turbomachine.
  • a turbomachine in particular a steam turbine, comprises a plurality of turbomachine blades as set out above.
  • Third embodiments of the subject matter disclosed herein relate to a method of forming protective structure.
  • a method of forming a protective structure on a turbomachine blade comprises the following successive steps: (A) providing a turbomachine blade comprising an airfoil portion having a leading edge and a trailing edge and first and second sides connecting the leading edge and the trailing edge, (B) forming a protective edging on the leading edge by laser cladding, and (C) forming first and second protective stripes on the first and second sides adjacently to the edging by cold spraying through at least one spraying nozzle.
  • Fig. 1 shows a schematic lateral view of an embodiment of a turbomachine blade before forming a protective structure
  • Fig. 2 shows a schematic lateral view of an embodiment of a turbomachine blade during formation of a protective structure
  • Fig. 3 shows a schematic lateral view of an embodiment of a turbomachine blade after forming a protective structure
  • Fig. 4 shows schematically a detail of Fig. 3
  • Fig. 5 shows schematically a cross-section view of Fig. 4;
  • Fig. 6 shows a schematic and partial cross-section view of an embodiment of a turbomachine blade before forming a protective structure
  • Fig. 7 shows a schematic and partial cross-section view of an embodiment of a turbomachine blade during formation of a protective structure (first intermediate stage);
  • Fig. 8 shows a schematic and partial cross-section view of an embodiment of a turbomachine blade during formation of a protective structure (second intermediate stage);
  • Fig. 9 shows a schematic and partial cross-section view of an embodiment of a turbomachine blade after forming a protective structure
  • Fig. 10 shows a schematic lateral view of an embodiment of a turbomachine blade after forming a protective structure in a way alternative to one of Fig. 3;
  • Fig. 1 1 shows first possible schematic and partial cross-section view of an embodiment of a turbomachine blade after forming a protective structure
  • Fig. 12 shows second possible schematic and partial cross-section view of an embodiment of a turbomachine blade after forming a protective structure
  • Fig. 13 shows third possible schematic and partial cross-section view of an embodiment of a turbomachine blade after forming a protective structure
  • Fig. 14 shows fourth possible schematic and partial cross-section view of an embodiment of a turbomachine blade after forming a protective structure.
  • Fig. 1 shows a schematic lateral view of a turbomachine blade 1 before forming a protective structure.
  • Blade 1 is provided with an airfoil portion 2 having a leading edge 3 and a trailing edge 4 as well as a first side 5 and a second side 6 (shown only in Fig. 5) connecting leading edge 3 and the trailing edge 4.
  • Airfoil portion 2 has a tip region 21 and a base region 22; base region 22 of airfoil portion 2 is adjacent to base portion 10 of blade 1.
  • Fig. 3, Fig. 4 and Fig. 5 show blade 1 after forming a protective structure.
  • the protective structure comprises a protective edging 7 (that may be called “bumper” or “buffer”) as well as a first protective stripe 8 and a second protective stripe 9 (shown only in Fig. 5); protective edging 7 is located on leading edge 3; first protective stripe 8 is located on first side 5 and adjacent to edging 7; second protective stripe 9 is located, preferably only, on second side 6 and adjacent to edging 7.
  • stripes 8 and 9 do not cover edging 7 and are located respectively only on sides 5 and 6.
  • stripes 8 and 9 are located respectively on sides 5 and 6, but cover also entirely edging 7; the thickness of stripes 8 and 9 reduces gradually on edging 7 and is zero (or close to zero) in the middle of edging 7.
  • the two stripes do not cover edging 171 and are located respectively only on the two sides of the airfoil.
  • the two stripes are located respectively on the two sides of the airfoil, but cover also partially edging 172; the thickness of the stripes reduces gradually on the edging and is zero (or close to zero) in the middle of the edging.
  • the two stripes are located respectively on the two sides of the airfoil, but cover also entirely edging 173; the thickness of the stripes reduces gradually on the edging and is minimum and low in the middle of the edging.
  • the two stripes are located respectively on the two sides of the airfoil, but cover also entirely edging 173; the thickness of the stripes reduces gradually on the edging and is minimum and high in the middle of the edging.
  • the edging of the protective structure protrudes from the leading edge of the airfoil portion of the blade. Protrusion (at the end of blade manufacturing) varies depending on the manufacturing process (e.g. degree of erosion due to cold spraying). Considering the camber line (100 in figures 1 1-14) of the airfoil portion and its prolongation, protrusion may be in the range of e.g. from 0.05 to 1 mm.
  • the cross-section area of the edging (immediately after its formation, e.g. before cold spraying) should take into account the manufacturing process (e.g. degree of erosion due to cold spraying) and may be in the range from 1 mm 2 to 20 mm 2 , more typically in the range from 4 mm 2 to 10 mm 2 .
  • the cross-section area of the edging (immediately after its formation, e.g. before cold spraying) should take into account the manufacturing process (e.g. degree of erosion due to cold spraying) and may look like a bulge.
  • the external shape of the airfoil portion of the blade at the end of blade manufacturing depends on the external shape of the airfoil portion of the blade before formation of the protective structure and on the overlying protective structure, in particular the protective edging and its erosion during formation of the protective stripes. Therefore, at least the leading edge of the airfoil portion of the blade before formation of the protective structure should be manufactured a bit recessed with respect to the ideal position of the leading edge of the airfoil portion of the blade at the end of blade manufacturing.
  • the solution according to the above embodiments is particular useful for thin blades, for example blades having a thin leading edge, for example in the range of 4-8 mm.
  • the edging of the protective structure is formed by laser cladding or welding or plasma spraying or detonation spraying or wire arc spraying or flame spraying or high velocity oxyfuel coating spraying or warm spraying (preferably by laser cladding), while the first and second stripes of the protective structure are formed by cold spraying.
  • the airfoil portion of the blade may be made of iron, titanium, nickel base alloy or stainless steel; preferably, it is made of stainless steel, for example AISI420.
  • the edging of the protective structure may be made of cobalt base alloy or cobalt-chromium alloy; preferably, it is made of Stellite-type material, in particular Stellite 6 or Stellite 12 or Stellite 21 , or Ultimet or any of the materials described and claimed in patent application EP1403397 or any of the materials described and claimed in patent application EP1403398.
  • the material of the edging is more resistant to solid particle erosion than the material of the airfoil in order to resist better to the mechanical erosion due to cold spraying.
  • the first and second stripes of the protective structure may be made of cobalt base alloy or cobalt-chromium alloy; preferably, they are made of Stellite-type material, in particular Stellite 6 or Stellite 12 or Stellite 21 , or Ultimet or any of the materials described and claimed in patent application EP1403397 or any of the materials described and claimed in patent application EP1403398.
  • the material of the first and second stripes is resistant to liquid droplet erosion.
  • the material of the first and second stripes may be equal to or different from the material of the edging.
  • the edging of the protective structure and the first and second stripes of the protective structure may extend over part (i.e. from preferably 20% to preferably 50%) of the height of the airfoil portion of the blade (see e.g. Fig. 3 and Fig. 10).
  • the head end of the stripes is at the tip of the airfoil portion and the tail end of stripes is at an intermediate position of the airfoil portion.
  • the edging of the protective structure is long equal to or slightly more than the first and second stripes of the protective structure.
  • the height of the airfoil portion being the portion of the blade extending from the tip to the root of the blade.
  • the first and second stripes of the protective structure may extend over part (i.e. from preferably 5% to preferably 50%) of the width of the airfoil portion of the blade (see e.g. Fig. 3 and Fig. 10).
  • the stripes extend from leading edge of the airfoil portion of the blade.
  • the width of the airfoil portion being the portion of the blade extending from the leading to the trailing edge.
  • Blades identical or similar to those that have just been described may advantageously be used in turbomachines in the fields of "Oil & Gas” and “Energy”.
  • steam turbines are an ideal application.
  • a protective structure identical or similar to those that have just been described may be formed on a turbomachine blade through the following successive steps:
  • turbomachine blade comprising an airfoil portion having a leading edge and a trailing edge and first and second sides connecting the leading edge and the trailing edge, (see e.g. Fig. 1 and Fig. 6)
  • a "thin leading edge” may have a thickness in the range of e.g. 2- 10 mm - as the cross-section of the leading edge is similar to a semicircle, a "thin leading edge” may have a radius in the range of e.g. 1-5 mm.
  • laser cladding Alternatively to laser cladding, one might use: welding or plasma spraying or detonation spraying or wire arc spraying or flame spraying or high velocity oxyfuel coating spraying or warm spraying.
  • the same spraying nozzle may be used for forming both protective stripes.
  • a first spraying nozzle may be used for forming a first protective stripe and a second spraying nozzle may be used for forming a second protective stripe; in this case, the first and second protective nozzles may be formed at the same time.
  • the stripes of the protective structure may comprise a plurality of parallel (or substantially parallel) segments.
  • segments 81 and 91 are transversal (specifically perpendicular) to the leading edge 3.
  • segments 181 are parallel (or substantially parallel) to the leading edge 103. It is to be noted that these segments touch each other laterally even if Fig. 4 and Fig. 10 show them as distant.
  • the spraying nozzle moves at least from a side (e.g. 5 or 6) of the airfoil portion toward the edging (e.g. 7) for forming a stripe (e.g. 8 or 9) and rotates preferably by at least 40° about the leading edge (e.g. 3) in order to form a stripe (e.g. 8 or 9) adjacent to the leading edge (e.g. 3) and to the edging (e.g. 7).
  • step C may comprise (consider e.g. figures 6-9):
  • a spraying nozzle moves from a first side (e.g. 5) of the airfoil portion toward the edging (e.g. 70, 71 , 72) and rotates by at least 40° and preferably 80-90° thus forming a segment (e.g. 81) of a first stripe (e.g. 8), and immediately after
  • a spraying nozzle moves from a second side (e.g. 6) of the airfoil portion toward the edging (e.g. 70, 71 , 72) and rotates by at least 40° and preferably 80-90° thus forming a segment (e.g. 91) of a second stripe (9); preferably, during sub-steps CIA and C2A the spraying nozzle maintains a constant longitudinal position on the airfoil portion.
  • step C may comprise:
  • a spraying nozzle moves from a first side (e.g.
  • the spraying nozzle maintains a constant longitudinal position on the airfoil portion, and the spraying nozzle is slightly displaced longitudinally after sub-step C IB and before sub-step C2B.
  • step C may comprise: - a first sub-step C3 wherein a spraying nozzle moves from the first side (e.g.
  • step C may comprise also the following sub- steps after sub -step C5 : - a fourth sub-step C6 wherein the same spraying nozzle moves from the second side (e.g. 6) of the airfoil portion toward the edging (e.g. 7) thus forming a segment of the second stripe (e.g. 9) adjacent to the previous one,
  • the spraying nozzle maintains a constant longitudinal position on the airfoil portion.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Structures Of Non-Positive Displacement Pumps (AREA)

Abstract

Une aube de turbomachine (1) comprend : une partie ayant un profil aérodynamique (2) et comportant un bord d'attaque (3), un bord de fuite (4) et des premier et second côtés (5, 6) reliant le bord d'attaque (3) au bord de fuite (4) ; et une structure de protection comportant une bordure de protection (7) ainsi que des première et seconde bandes de protection (8, 9). La bordure de protection (7) est située sur le bord d'attaque (3). La première bande de protection (8) est située sur le premier côté de protection (5) et à côté de la bordure (7). La seconde bande de protection (9) est située sur le second côté de protection (6) et à côté de la bordure (7). La bordure (7) est formée par placage ou soudage au laser, par pulvérisation à plasma, par pulvérisation par détonation, par projection à l'arc-fil, par projection à la flamme, par projection de revêtement à grande vitesse par oxyfuel ou par projection à chaud. Les première et seconde bandes (8, 9) sont formées par projection à froid.
PCT/EP2016/066445 2015-07-13 2016-07-11 Aube de turbomachine à structure de protection, turbomachine et procédé de formation d'une structure de protection WO2017009295A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP16736885.1A EP3322832B1 (fr) 2015-07-13 2016-07-11 Procédé de formation d'une structure de protection sur une aube de turbomachine
PL16736885T PL3322832T3 (pl) 2015-07-13 2016-07-11 Sposób formowania struktury zabezpieczającej na łopatce maszyny wirnikowej
BR112018000669-6A BR112018000669B1 (pt) 2015-07-13 2016-07-11 Método de formação de uma estrutura de proteção em uma lâmina de turbo-máquina
JP2017567771A JP6847059B2 (ja) 2015-07-13 2016-07-11 保護構造を有するターボ機械のブレード、ターボ機械、および保護構造を形成する方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT102015000033498 2015-07-13
ITUB2015A002136A ITUB20152136A1 (it) 2015-07-13 2015-07-13 Pala di turbomacchina con struttura protettiva, turbomacchina, e metodo per formare una struttura protettiva

Publications (1)

Publication Number Publication Date
WO2017009295A1 true WO2017009295A1 (fr) 2017-01-19

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2016/066445 WO2017009295A1 (fr) 2015-07-13 2016-07-11 Aube de turbomachine à structure de protection, turbomachine et procédé de formation d'une structure de protection

Country Status (6)

Country Link
EP (1) EP3322832B1 (fr)
JP (1) JP6847059B2 (fr)
BR (1) BR112018000669B1 (fr)
IT (1) ITUB20152136A1 (fr)
PL (1) PL3322832T3 (fr)
WO (1) WO2017009295A1 (fr)

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CN110439623A (zh) * 2019-08-14 2019-11-12 上海两擎机电科技合伙企业(有限合伙) 飞机发动机风扇叶片用金属包边、加工工装及加工方法
WO2020128391A1 (fr) * 2018-12-21 2020-06-25 Safran Procede de fabrication d'un noyau
CN111793795A (zh) * 2020-06-24 2020-10-20 浙江工业大学 一种基于加工硬化塑性沉积的钴基抗汽蚀涂层的制备方法

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CN111020562B (zh) * 2019-12-09 2021-07-20 山东建筑大学 一种激光制备非晶与碳基纳米相增强复合材料的方法

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FR3090427A1 (fr) * 2018-12-21 2020-06-26 Safran Procede de fabrication d’un noyau
CN110439623A (zh) * 2019-08-14 2019-11-12 上海两擎机电科技合伙企业(有限合伙) 飞机发动机风扇叶片用金属包边、加工工装及加工方法
CN110439623B (zh) * 2019-08-14 2024-05-14 上海两擎机电科技合伙企业(有限合伙) 飞机发动机风扇叶片用金属包边、加工工装及加工方法
CN111793795A (zh) * 2020-06-24 2020-10-20 浙江工业大学 一种基于加工硬化塑性沉积的钴基抗汽蚀涂层的制备方法

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JP2018527500A (ja) 2018-09-20
EP3322832B1 (fr) 2021-08-25
ITUB20152136A1 (it) 2017-01-13
PL3322832T3 (pl) 2021-12-27
BR112018000669B1 (pt) 2021-12-14
JP6847059B2 (ja) 2021-03-24
BR112018000669A2 (pt) 2018-09-18

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