EP3201370B1 - Produit corroye en alliage aluminium magnesium lithium - Google Patents

Produit corroye en alliage aluminium magnesium lithium Download PDF

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Publication number
EP3201370B1
EP3201370B1 EP15785159.3A EP15785159A EP3201370B1 EP 3201370 B1 EP3201370 B1 EP 3201370B1 EP 15785159 A EP15785159 A EP 15785159A EP 3201370 B1 EP3201370 B1 EP 3201370B1
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product
weight
wrought
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mpa
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German (de)
English (en)
French (fr)
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EP3201370A1 (fr
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Gaëlle POUGET
Bernard Bes
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Constellium Issoire SAS
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Constellium Issoire SAS
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Priority claimed from FR1402187A external-priority patent/FR3026410B1/fr
Priority claimed from FR1402186A external-priority patent/FR3026411B1/fr
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/047—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with magnesium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
    • C22C21/08—Alloys based on aluminium with magnesium as the next major constituent with silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor

Definitions

  • the invention relates to wrought aluminum-magnesium-lithium alloy products, more particularly such products with an improved compromise in properties, in particular an improved compromise between tensile elastic limit and toughness of said products.
  • the invention also relates to a manufacturing process as well as the use of these products intended in particular for aeronautical and aerospace construction.
  • Wrought aluminum alloy products are developed to produce high strength parts intended in particular for the aeronautical industry and the aerospace industry.
  • Aluminum alloys containing lithium are very interesting in this regard, since lithium can reduce the density of aluminum by 3% and increase the modulus of elasticity by 6% for each weight percent of lithium added.
  • aluminum alloys containing simultaneously magnesium and lithium make it possible to achieve particularly low densities and have therefore been extensively studied.
  • the patent GB 1,172,736 teaches an alloy containing 4 to 7% by weight Mg, 1.5 - 2.6% Li, 0.2 - 1% Mn and / or 0.05 - 0.3% Zr, aluminum residue, useful for processing of products with high mechanical strength, good corrosion resistance, low density and high elastic modulus. Said products are obtained by a process comprising an optional quenching followed by tempering.
  • the products resulting from the process according to GB 1,172,736 have a tensile strength ranging from approximately 440 MPa to approximately 490 MPa, a tensile elastic limit ranging from approximately 270 MPa to approximately 340 MPa and an elongation at rupture of the order of 5-8%.
  • This document also discloses a process for obtaining said alloy comprising the steps: a) pouring an ingot of the composition described above, b) removing the residual stresses from said ingot by heat treatment, c) homogenizing by heating and maintaining temperature then cool the ingot, d) hot roll said ingot to its final thickness, e) dissolve and then soak the product thus laminated, f) tract the product and g) achieve an income of said product by heating and maintaining temperature .
  • the patent US 5,431,876 teaches a group of ternary aluminum alloys lithium and magnesium or copper, including at least one additive such as zirconium, chromium and / or manganese.
  • the alloy is prepared according to methods known to a person skilled in the art, comprising, for example, extrusion, dissolving, quenching, pulling the product from 2 to 7% and then tempering.
  • the patent US 6,551,424 describes a process for manufacturing rolled aluminum-magnesium-lithium alloy products with a composition (in% by weight) Mg: 3.0 - 6.0; Li: 0.4 - 3.0; Zn up to 2.0; Mn up to 1.0; Ag up to 0.5; Fe up to 0.3; If up to 0.3; Cu up to 0.3; 0.02 - 0.5 of an element selected from the group consisting of Sc, Hf, Ti, V, Nd, Zr, Cr, Y, Be, said method including cold rolling lengthwise and in the sense of width.
  • the patent US 6,461,566 describes an alloy of composition (in% by weight) Li: 1.5 - 1.9; Mg: 4.1 - 6.0; Zn 0.1 - 1.5; Zr 0.05 - 0.3; Mn 0.01 - 0.8; H 0.9 x 10 -5 - 4.5 x 10 -5 and at least one element selected from the group Be 0.001 - 0.2; Y 0.001 - 0.5 and Sc 0.01 - 0.3.
  • the patent application WO 2012/16072 describes a wrought aluminum alloy product of composition in% by weight, Mg: 4.0 - 5.0; Li: 1.0 - 1.6; Zr: 0.05-0.15; Ti: 0.01 - 0.15; Fe: 0.02 - 0.2; If: 0.02 - 0.2; Mn: ⁇ 0.5; Cr ⁇ 0.5; Ag: ⁇ 0.5; Cu ⁇ 0.5; Zn ⁇ 0.5; Sc ⁇ 0.01; other items ⁇ 0.05; remains aluminum.
  • Said product is in particular obtained according to a manufacturing process comprising in particular successively the casting of the alloy in raw form, its deformation hot and optionally cold, the dissolution then the quenching of the product thus deformed, optionally the cold deformation of the product thus put in solution and quenched and finally the tempering of the product wrought at a temperature below 150 ° C.
  • the metallurgical state obtained for the rolled products is advantageously a T6 or T6X or T8 or T8X state and for the extruded products advantageously a T5 or T5X state in the case of press quenching or a T6 or T6X or T8 or T8X state.
  • Wrought aluminum-magnesium-lithium alloy products have a low density and are therefore particularly interesting in the extremely demanding field of aeronautics.
  • their performance must be significantly improved compared to that of existing products, in particular their performance in terms of compromise between the properties of static mechanical resistance (in particular tensile elastic limit and in compression, resistance to rupture) and the properties of tolerance to damage (toughness, resistance to the propagation of cracks in fatigue), these properties being in general contradictory.
  • These alloys must also have sufficient corrosion resistance, be able to be shaped according to the usual methods and have low residual stresses so that they can be machined without substantial distortion during said machining.
  • a first object of the invention is a wrought aluminum alloy product of composition, in% by weight, Mg: 4.0 - 5.0; Li: 1.0 - 1.8; Mn: 0.35 - 0.45; Zr: 0.05-0.15; Ag: ⁇ 0.5; Fe: ⁇ 0.1; Ti: ⁇ 0.15; If: ⁇ 0.05; other elements ⁇ 0.05 each and ⁇ 0.15 in combination; remains aluminum.
  • Another subject of the invention is the use of said wrought product to produce an aircraft structural element.
  • the static mechanical characteristics in tension in other words the tensile strength R m , the conventional elastic limit at 0.2% elongation R p0.2 , and the elongation at break A%, are determined by a tensile test according to standard NF EN ISO 6892-1, the sampling and the direction of the test being defined by standard EN 485-1.
  • the toughness is determined by a toughness test K1c according to standard ASTM E399.
  • a curve giving the effective stress intensity factor as a function of the effective crack extension is determined according to standard ASTM E399.
  • the results were also presented in K max (stress intensity factor corresponding to the maximum force P max ).
  • the increase in stresses on the product during the K1c toughness test according to ASTM E399 may be indicative of the propensity of the product to delamination.
  • delamination (“crack delamination” and / or “crack divider” in English) is understood here to mean cracking in planes orthogonal to the front of the main crack. The orientation of these plans corresponds to that of grain boundaries not recrystallized after deformation by wrought. Low delamination is a sign of less fragility in the planes concerned and minimizes the risk of crack deviation towards the longitudinal direction during propagation in fatigue or under monotonous stress.
  • a structural element or a structural element of a mechanical construction is called a mechanical part for which the static and / or dynamic mechanical properties are particularly important for the performance of the structure and for which a structural calculation is usually prescribed or performed.
  • These are typically elements whose failure is likely to endanger the safety of said construction, its users, its users or others.
  • these structural elements include in particular the elements that make up the fuselage (such as the fuselage skin, the stiffeners or stringers of the fuselage (stringers), the bulkheads, the frames of fuselage (circumferential frames), the wings (such as upper or lower wing skin), stiffeners (stringers or stiffeners), ribs (ribs), spars, floor beams and the seat rails) and the tail unit composed in particular of horizontal and vertical stabilizers (horizontal or vertical stabilizers), as well as the doors.
  • the fuselage such as the fuselage skin, the stiffeners or stringers of the fuselage (stringers), the bulkheads, the frames of fuselage (circumferential frames), the wings (such as upper or lower wing skin), stiffeners (stringers or stiffeners), ribs (ribs), spars, floor beams and the seat rails
  • the tail unit composed in particular of horizontal and vertical stabilizers (horizontal or vertical stabilizers), as well as the doors.
  • the wrought aluminum alloy product according to the invention has the following particular composition, in% by weight: Mg: 4.0 - 5.0; Li: 1.0 - 1.8; Mn: 0.35 - 0.45; Zr: 0.05 - 0, 15; Ag: ⁇ 0.5; Fe: ⁇ 0.1; Ti: ⁇ 0.15; Si: ⁇ 0.05; other elements ⁇ 0.05 each and ⁇ 0.15 in combination aluminum alloy products having such a composition associated in particular with the particular Mn content selected exhibit improved static mechanical properties as well as a low propensity for delamination.
  • the Mn content, in% by weight is preferably from 0.35 to 0.40.
  • the raw form of aluminum alloy has a silver content of less than or equal to 0.25% by weight, more preferably a silver content of 0.05% to 0.1% by weight.
  • This element contributes in particular to static mechanical properties.
  • the shape crude aluminum alloy has a total Ag and Cu content of less than 0.15% by weight, preferably less than or equal to 0.12%. Control of the maximum content of these two elements in combination makes it possible in particular to improve the resistance to intergranular corrosion of the wrought product.
  • the raw form has a zinc content, in% by weight, of less than 0.04%, preferably less than or equal to 0.03%.
  • a zinc content in% by weight, of less than 0.04%, preferably less than or equal to 0.03%.
  • the raw aluminum alloy form has an Fe content, in% by weight, of less than 0.08%, preferably less than or equal to 0.07%, more preferably still less than or equal to 0.06%.
  • the present inventors believe that a minimum content of Fe, and possibly that of Si, can contribute to improving the mechanical properties and in particular the fatigue properties of the alloy. Excellent results have in particular been obtained for an Fe content of 0.02 to 0.06% by weight and / or an Si content of 0.02 to 0.05% by weight.
  • the lithium content of the products according to the invention is between 1.0 and 1.8% by weight.
  • the crude form of aluminum alloy has a Li content, in% by weight, less than 1.6%, preferably less than or equal to 1.5%, preferably still less than or equal to 1 , 4%.
  • a minimum lithium content of 1.1% by weight and preferably 1.2% by weight is advantageous.
  • the present inventors have found that a limited lithium content, in the presence of certain addition elements, makes it possible to very significantly improve the toughness, which largely compensates for the slight increase in density and the decrease in static mechanical properties.
  • the raw form of aluminum alloy has a Zr content, in% by weight, of 0.10 to 0.15%.
  • the inventors have indeed found that such a Zr content makes it possible to obtain an alloy having a favorable fiber structure for improved static mechanical properties.
  • the raw form of aluminum alloy has an Mg content, in% by weight, of 4.5 to 4.9%. Excellent results have been obtained for alloys according to this embodiment in particular with regard to static mechanical properties.
  • the Cr content of the products according to the invention is less than 0.05% by weight, preferably less than 0.01% by weight.
  • Such a limited Cr content in combination with the other elements of the alloy according to the invention makes it possible in particular to limit the formation of primary phases during casting.
  • the Ti content of the products according to the invention is less than 0.15% by weight, preferably between 0.01 and 0.05% by weight.
  • the Ti content is limited in the particular alloy of the present invention, in particular to avoid the formation of primary phases during casting. On the other hand, it may be advantageous to control the Ti content to control the granular structure and in particular the grain size during the casting of the alloy.
  • the products according to the invention have a maximum content of 10 ppm of Na, preferably of 8 ppm of Na, and / or a maximum content of 20 ppm of Ca.
  • the raw form of aluminum alloy is substantially free of Sc, Be, Y, more preferably said raw form comprises less than 0.01% by weight of these elements taken in combination.
  • the process for manufacturing the products according to the invention comprises the successive stages of preparing a bath of liquid metal so as to obtain an Al-Mg-Li alloy of particular composition, the casting of said alloy in raw form, optionally the homogenization of said raw form thus cast, the hot deformation of said raw form to obtain a hot deformed product, optionally dissolving the product thus hot deformed, quenching of said hot deformed product, optionally dressing / leveling of the deformed and quenched product, optionally the cold deformation in a controlled manner of the deformed and quenched product to obtain a permanent cold deformation of 1 to 10%, preferably 2 to 6%, more preferably still 3 to 5%, the income of said deformed and quenched product.
  • the tempering step is carried out before the cold deformation step in a controlled manner.
  • the manufacturing process therefore firstly consists in casting a raw form of Al-Mg-Li alloy with a composition, in% by weight: Mg: 4.0 - 5.0; Li: 1.0 -1.8; Mn: 0.35 - 0.45; Zr: 0.05-0.15; Ag: ⁇ 0.5; Fe: ⁇ 0.1; Ti: ⁇ 0.15; If: ⁇ 0.05; other elements ⁇ 0.05 each and ⁇ 0.15 in combination; remains aluminum.
  • a bath of liquid metal is therefore produced and then poured in raw form, typically a rolling plate, a spinning billet or a forge blank.
  • the manufacturing process optionally includes a step of homogenizing the raw form so as to reach a temperature between 450 ° C and 550 ° C and, preferably, between 480 ° C and 520 ° C for a period of between 5 and 60 hours.
  • the homogenization treatment can be carried out in one or more stages.
  • the hot deformation is carried out directly following a simple reheating without carrying out homogenization.
  • the raw form is then deformed when hot, typically by spinning, rolling and / or forging, to obtain a deformed product.
  • This hot deformation is preferably carried out at an inlet temperature above 400 ° C and, advantageously, from 420 ° C to 450 ° C.
  • the hot deformation is a deformation by spinning of the raw form.
  • the product deformed hot and, optionally cold, is optionally subjected to a separate dissolution at a temperature of 360 ° C to 460 ° C, preferably from 380 ° C to 420 ° C, for 15 minutes to 8 hours.
  • the deformed product and, optionally, dissolved, is then quenched.
  • the quenching is carried out with water and / or air. It is advantageous to carry out air quenching because the intergranular corrosion properties are improved.
  • it is advantageous to carry out quenching on a press (or quenching on spinning heat), preferably a quenching on an air press, such quenching making it possible in particular to improve the static mechanical properties .
  • it can also be a quenching on a water press.
  • the product is dissolved in heat on spinning.
  • the hot deformed and quenched product can optionally be subjected to a dressing or leveling step depending on whether it is a profile or a sheet.
  • dressing or leveling is understood here to mean a cold deformation step without permanent deformation or with a permanent deformation of less than 1%.
  • the product hot deformed, quenched and, optionally upright / planed, is also cold deformed in a controlled manner to obtain a permanent cold deformation of 1 to 10%, preferably 2 to 6%, more preferably still 3 to 5 %, and more preferably still from 4 to 5%.
  • the permanent cold deformation is 2 to 4%.
  • Cold deformation can in particular be carried out by traction, compression and / or rolling. According to a preferred embodiment, the cold deformation is carried out by traction.
  • the deformed, hardened and optionally straightened / leveled product undergoes a tempering stage.
  • the tempering is carried out by heating, in one or more stages, at a temperature below 150 ° C, preferably at a temperature of 70 ° C to 140 ° C, for 5 to 100 hours.
  • the tempering step is carried out after the cold deformation step in a controlled manner.
  • the metallurgical state obtained for the wrought products corresponds in particular to a T8 state according to standard EN515.
  • the tempering step is carried out before the cold deformation step in a controlled manner.
  • the product hot deformed and tempered is then cold deformed in a controlled manner to obtain a permanent cold deformation of 1 to 10%, preferably 2 to 6%, more preferably still 3 to 5%, and more preferably still 4 to 5%.
  • the permanent cold deformation is 2 to 4%.
  • the method for manufacturing a wrought product does not include any cold deformation step inducing a permanent deformation of at least 1% between the hot deformation step or, if this step is present, solution and the income stage.
  • the combination of the chosen composition, in particular of the content of Mg, Li and Mn and of the processing parameters, in particular the order of the stages of the manufacturing process, advantageously makes it possible to obtain wrought products having an improved compromise in properties. very particular, especially the compromise between mechanical resistance and tolerance to damage, while having a low density and good corrosion performance.
  • the wrought products according to the invention are preferably spun products such as profiles, rolled products such as sheets or thick sheets and / or forged products.
  • the wrought products according to the invention have particularly advantageous characteristics in comparison with identical wrought products but having the only difference in their Mn content, in particular an Mn content, in% by weight, of less than 0.3% or greater than 0.5%.
  • identical wrought products means aluminum alloy products of the same composition, in% by weight, with the exception of Mn, and obtained according to the same manufacturing process, in particular wrought products in the same metallurgical state. according to standard EN515 and having the same rate of deformation in permanent traction in traction obtained by traction in a controlled manner.
  • the wrought products according to the invention exhibit less delamination on the rupture surfaces of the K1c test pieces obtained according to ASTM E399 than identical wrought products but having the only difference in their Mn content, in particular a Mn content, in% by weight, less than 0.3% or more than 0.5%.
  • the wrought products according to the invention have at mid-thickness, for a thickness between 0.5 and 15 mm, a tensile strength Rm (L) greater than that of products identical wrought but with the only difference being their Mn content, in particular an Mn content, in% by weight, less than 0.3% or more than 0.5%.
  • the wrought products according to the invention have, at mid-thickness, for a thickness between 0.5 and 15 mm, a yield strength in tension Rp0,2 (L) higher than that of identical wrought products but having the only difference in their Mn content, in particular an Mn content, in% by weight, less than 0.3% or more than 0.5%.
  • the products wrought in the T8 or T9 state mentioned above have, for a thickness of between 0.5 and 15 mm, at mid-thickness at least two properties of static mechanical resistance chosen from the properties ( i) to (iii) and at least one damage tolerance property chosen from properties (iv) to (v).
  • the products spun according to the invention have particularly advantageous characteristics.
  • the spun products preferably have a thickness of between 0.5 mm and 15 mm, but products with a thickness greater than 15 mm, up to 50 mm or even 100 mm or more may also have advantageous properties.
  • the thickness of the extruded products is defined according to standard EN 2066: 2001: the cross section is divided into elementary rectangles of dimensions A and B; A being always the largest dimension of the elementary rectangle and B being able to be considered as the thickness of the elementary rectangle. The sole is the elementary rectangle with the largest dimension A.
  • the wrought products according to the invention are advantageously used to produce structural elements for aircraft, in particular for aircraft.
  • Preferred aircraft structural elements are in particular a fuselage skin, a fuselage frame, a stiffener or a fuselage beam or even a wing skin, a wing stiffener, a rib or a spar.
  • Alloy B has a composition according to the invention.
  • the density of alloys A and B calculated in accordance with the procedure of The Aluminum Association described on pages 2-12 and 2-13 of "Aluminum Standards and Data", is 2.55.
  • B 0.11 1.39 0.03 0.06 0.01 0.03 0.41 4.57 0.03 0.11 8 15 2.55
  • Alloy B has a composition according to the invention.
  • the values of K Q have always been invalid according to the ASTM E399 standard, in particular with respect to the criterion P max / P Q ⁇ 1.10. For this, the results are presented in K max (stress intensity factor corresponding to the maximum force P max ).
  • the results are reported in Tables 6 and 7 and illustrated in figures 2 and 3 (LT and TL test pieces respectively). These results are the means of at least two 2 values.
  • the products according to the invention have a satisfactory toughness whatever the Mn content of the alloy.
  • the figure 2 illustrates the elastic limit, Rp0,2, of the products of this example as a function of the toughness, K Q (all the values of K Q are invalid due to the criterion P max / P Q ⁇ 1.10).
  • the figure 3 illustrates the elastic limit, Rp0,2, of the products of this example as a function of the stress intensity factor corresponding to the maximum stress, K max .
  • the products in T9 exhibit an excellent compromise between their static properties, in particular Rp0.2, and their toughness, K Q , or their stress intensity factor corresponding to the maximum force, K max .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
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EP15785159.3A 2014-09-29 2015-09-29 Produit corroye en alliage aluminium magnesium lithium Active EP3201370B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR1402187A FR3026410B1 (fr) 2014-09-29 2014-09-29 Produit corroye en alliage aluminium magnesium lithium
FR1402186A FR3026411B1 (fr) 2014-09-29 2014-09-29 Procede de fabrication de produits en alliage aluminium magnesium lithium
PCT/FR2015/052580 WO2016051060A1 (fr) 2014-09-29 2015-09-29 Produit corroye en alliage aluminium magnesium lithium

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EP3201370A1 EP3201370A1 (fr) 2017-08-09
EP3201370B1 true EP3201370B1 (fr) 2020-04-15

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EP15785159.3A Active EP3201370B1 (fr) 2014-09-29 2015-09-29 Produit corroye en alliage aluminium magnesium lithium

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US (2) US20170292180A1 (ko)
EP (2) EP3201371B1 (ko)
JP (1) JP2017532456A (ko)
KR (1) KR20170067810A (ko)
CN (2) CN106715735A (ko)
BR (2) BR112017006273B1 (ko)
CA (2) CA2960947A1 (ko)
WO (2) WO2016051061A1 (ko)

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FR3057476B1 (fr) * 2016-10-17 2018-10-12 Constellium Issoire Toles minces en alliage aluminium-magnesium-scandium pour applications aerospatiales
CA3040622A1 (en) 2016-10-24 2018-05-03 Shape Corp. Multi-stage aluminum alloy forming and thermal processing method for the production of vehicle components
FR3080861B1 (fr) * 2018-05-02 2021-03-19 Constellium Issoire Procede de fabrication d'un alliage aluminium cuivre lithium a resistance en compression et tenacite ameliorees
CA3134698A1 (en) * 2019-04-05 2020-10-08 Arconic Technologies Llc Methods of cold forming aluminum lithium alloys
CA3163346C (en) * 2019-12-17 2024-05-21 Novelis Inc. Suppression of stress corrosion cracking in high magnesium alloys through the addition of calcium
CN112226656A (zh) * 2020-09-25 2021-01-15 西南铝业（集团）有限责任公司 一种Al-Mg-Mn-Er系铝合金挤压制品的生产工艺
CN112410691B (zh) * 2020-11-10 2021-12-24 中国航发北京航空材料研究院 一种铝锂合金材料退火工艺
CN114054531A (zh) * 2021-11-18 2022-02-18 西南铝业（集团）有限责任公司 一种高均匀性2196铝锂合金型材的挤压方法

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CA2960947A1 (fr) 2016-04-07
BR112017006131A2 (pt) 2017-12-19
BR112017006273A2 (pt) 2017-12-12
EP3201371A1 (fr) 2017-08-09
EP3201371B1 (fr) 2021-04-28
KR20170067810A (ko) 2017-06-16
EP3201370A1 (fr) 2017-08-09
WO2016051061A1 (fr) 2016-04-07
US20170218493A1 (en) 2017-08-03
BR112017006273B1 (pt) 2021-06-08
CA2960942A1 (fr) 2016-04-07
CN107075623A (zh) 2017-08-18
JP2017532456A (ja) 2017-11-02
CN106715735A (zh) 2017-05-24
US20170292180A1 (en) 2017-10-12
WO2016051060A1 (fr) 2016-04-07

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