WO2016120816A1 - Method for the production of superconductors - Google Patents

Method for the production of superconductors Download PDF

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Publication number
WO2016120816A1
WO2016120816A1 PCT/IB2016/050425 IB2016050425W WO2016120816A1 WO 2016120816 A1 WO2016120816 A1 WO 2016120816A1 IB 2016050425 W IB2016050425 W IB 2016050425W WO 2016120816 A1 WO2016120816 A1 WO 2016120816A1
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WO
WIPO (PCT)
Prior art keywords
sheet
blank
powder
wire
superconductors
Prior art date
Application number
PCT/IB2016/050425
Other languages
French (fr)
Inventor
Giovanni Grasso
Davide Nardelli
Maurizio Vignolo
Mustafa Akdogan
Hakan YETIS
Original Assignee
Columbus Superconductors S.P.A.
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 Columbus Superconductors S.P.A. filed Critical Columbus Superconductors S.P.A.
Publication of WO2016120816A1 publication Critical patent/WO2016120816A1/en

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Classifications

    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00Superconducting devices
    • H10N60/01Manufacture or treatment
    • H10N60/0856Manufacture or treatment of devices comprising metal borides, e.g. MgB2

Definitions

  • the present invention relates to a method for the production of superconductors. More in particular, the method according to present invention relates to the production of simple or composite wires made of magnesium diboride (MgB2). Such a method is applied to the production of electromagnets used in the most varied sectors and of wires for transporting electrical currents.
  • sectors include the medical field (in magnetic resonance imaging machines) and the field of experimental physics (in particle accelerators).
  • Such wires are normally used in cryogenic conditions, at temperatures of use typically comprised between 4 Kelvin and 40 Kelvin, temperatures at which magnesium diboride becomes superconducting.
  • an operator manually introduces the correct stoichiometric quantities of powders into an agitator typically of mechanical type, such as a planetary ball mill system, in which the rotation of appropriately filled jars causes the Mg and B powders to knock into each other, against the inner walls and against some metal balls contained therein.
  • an agitator typically of mechanical type, such as a planetary ball mill system, in which the rotation of appropriately filled jars causes the Mg and B powders to knock into each other, against the inner walls and against some metal balls contained therein.
  • the step of mixing of the powders is very delicate not only, as mentioned, for the need to obtain a homogenous mixture free from undesired contaminants, but also because all the steps in which the operator must handle the powders must be carried out in closed environments, to operate inside which the operators must insert their hands in specific fixed gripping gloves through the security glass which separates the operator from the working environment.
  • the operator fills a tube made of metal or appropriate alloy with the mixed powders (billet).
  • a billet is thus mechanically deformed, typically by drawing and/or rolling processes as needed, to produce a superconductor wire of smaller diameter and greater length than the initial one.
  • the wire is subjected to a thermal treatment so as to trigger the reaction between the boron and the magnesium and thus make the magnesium-diboride- based compound inside the metal or alloy sheath which constituted the initial containing tube.
  • MgB2 superconductors starting from mixing powders implies a substantial risk of lack of uniformity inside the material.
  • a prevalence of boron or of magnesium powder may be created in some zones. Consequently, such a material in excess does not react and remains as impurity in the superconductor.
  • the aforesaid thermal reaction causes the formation of a spongiform MgB2 structure, in which the superconductor particles are surrounded by holes, which may result as interruptions of continuity of the superconductor structure, thus significantly limiting the electrical properties.
  • the technical task underlying the present invention is to suggest a method for the production of superconductors which overcomes the drawbacks of the prior art mentioned above.
  • the technical task and the specified objects are substantially achieved by a method for the production of superconductors comprising the technical features illustrated in one or more of the appended claims.
  • the method for the production of superconductors according to the present invention comprises a step of preparing a sheet of a first material.
  • a first material is preferably magnesium, either pure or possibly with the addition of impurities chosen and controlled to increase the transporting properties or the mechanical properties.
  • the sheet has a longitudinal development axis.
  • a predetermined amount of powder of a second material is thus dosed.
  • a second material is preferably boron, either pure or possibly with the addition of impurities chosen and controlled to increase the transporting properties or the mechanical properties.
  • Such a powder is spread on the sheet according to a predetermined dosing so as to define a layer of second material.
  • the dosing is performed according to a stoichiometric ratio Mg:B of 1 :2, except for variations which take dopants or additives into account.
  • Such a step of wrapping may comprise the sub-step of preparing a support having a prevalent development axis parallel to the longitudinal development axis.
  • the sheet is thus wrapped to obtain a blank.
  • Such a blank is then processed by drawing and rolling to turn it into a wire.
  • the wire is then thermally treated to obtain the formation of the MgB2 superconductor by means of the reaction between the boron powders and the magnesium sheet.
  • the superconductor resulting from the method according to the present invention will have an internal spiral structure.
  • Such a structures is basically more uniform than that known until now in the prior art, and also has considerably improved mechanical properties, because the voids present are uniformly distributed along the length and the spacing between the planes of the spiral allows movements of the MgB2 planes without causing the creation of fractures caused by the bending of the wire.
  • FIG. 2 diagrammatically shows a second step of the method for the production of superconductors according to the present invention.
  • FIG. 3 diagrammatically shows a third step of the method for the production of superconductors according to the present invention.
  • figure 1 shows a step of preparing a sheet 1 of a first material.
  • a first material is preferably magnesium.
  • the sheet has a longitudinal development axis "A". More in particular, the sheet 1 has a rectangular shape. In different embodiments of the invention, the development axis "A" may be defined in parallel to the either longer side or shorter side of the sheet 1 .
  • a predetermined amount of powder of a second material is thus dosed.
  • a second material is preferably boron.
  • Such a powder is spread on the sheet 1 according to a predetermined dosing to define a layer 2 of second material. Dosing occurs in particular according to a stoichiometric ratio between the first and the second material 1 :2.
  • the distribution of the second material on the sheet 1 may be carried out homogeneously, e.g. by roughly applying the powder and then distributing it with a predetermined spacer.
  • a pressure can be applied (e.g. by means of a metal surface) on the layer 2 so as to compact the powder and make it adhere to the surface of the sheet 1 in a preliminary manner so as to wrap it.
  • a further sheet of material is added and pressed on the layer 2 to define a containment for the powders.
  • the powders of second material may be mixed with an appropriate substance which is easily evaporable but not water-based, such as, for example ultra-pure isopropyl alcohol, which may help to spread the powders of second material uniformly on the sheet 1 .
  • the added liquid may be subsequently removed by evaporation either at ambient temperature or at higher temperature, possibly in vacuum conditions to accelerate the process.
  • the uniform spreading of the layer 2 is facilitated and the required position and size of the layer 2 is maintained.
  • the sheet 1 covered with the layer of powder 2 is wrapped along the longitudinal development axis "A" to obtain a blank 3.
  • Such a step of wrapping may comprise the sub-step of preparing a support 4 having a prevalent development axis "B" parallel to the longitudinal development axis "A".
  • the sheet 1 may be wound on such a support 4.
  • the support is a wire or a tube.
  • such a support 4 may also have a function of improving the mechanical and/or electrical properties of the wire once completed.
  • the method comprises the further step of inserting the blank 3 in a casing 7.
  • a casing 7 comprises a tube, preferably cylindrical, having a cavity 7a adapted to house the blank.
  • the casing 7 is preferably made of steel, or of various alloys, in particular nickel-based. It is worth noting that, according to with the present invention, the step of inserting the blank 3 inside the casing 7 is carried out before the step of thermal treating.
  • the blank 3 is subjected to drawing to obtain a wire 5.
  • a wire 5 may be cut, in turn, into a plurality of pieces of predetermined length.
  • the wires 5 may thus be stacked again, according to a predetermined mode, and re- introduced into a further casing (not shown).
  • the assembly may be processed again in manner similar to the wire 5, so as to obtain a wire comprising a plurality of MgB2 cores, named "multifilamentary" wire in the technical jargon of the sector.
  • the blank 3 is thus thermally treated to obtain a wire 5 of superconductor 6.
  • such a superconductor is magnesium diboride.
  • the thermal treatment cycle comprises at least one step in which the wire 5 is taken to a temperature higher than the melting temperature of magnesium.
  • the sheet 1 passes either partially or totally to the liquid state and, by reacting with the boron powder, produces the superconductor 6 uniformly along the entire wire 5.
  • the method further comprises a step of pressurizing of the blank 3, during the thermal treatment or subsequently thereafter.
  • a mechanical or pneumatic pressure is exerted externally to the wire 5 on the surface thereof so as to compress the external diameter.
  • this allows to either reduce or eliminate possible areas devoid of superconductor inside the wire 5.
  • a plurality of pieces of a plurality of pieces of blank 3 can be inserted inside a further casing (not shown).
  • a further casing is thus pressurized and thermally treated.
  • the further casing filled with the pieces of blank 3 may be processed in manner similar to the blank 3 itself, so as to obtain a wire comprising a plurality of MgB2 cores.

Abstract

A method for the production of superconductors, comprises the steps of: preparing a sheet (1 ) of a first material having a longitudinal development axis (A); dosing a predetermined amount of powder of a second material; spreading the powder on the sheet (1 ) to define a layer (2) of said second material; wrapping the sheet along the longitudinal axis (A) to obtain a blank (3); mechanically processing such a blank to obtain a wire; thermally treating the wire to make the boron and the magnesium react in order to obtain MgB2.

Description

METHOD FOR THE PRODUCTION OF SUPERCONDUCTORS Field of the invention
The present invention relates to a method for the production of superconductors. More in particular, the method according to present invention relates to the production of simple or composite wires made of magnesium diboride (MgB2). Such a method is applied to the production of electromagnets used in the most varied sectors and of wires for transporting electrical currents. By way of example only, sectors include the medical field (in magnetic resonance imaging machines) and the field of experimental physics (in particle accelerators).
Prior art
It is known to produce wires made of superconductor material, in particular of magnesium diboride (MgB2).
Such wires are normally used in cryogenic conditions, at temperatures of use typically comprised between 4 Kelvin and 40 Kelvin, temperatures at which magnesium diboride becomes superconducting.
In the known method of production, an operator manually introduces the correct stoichiometric quantities of powders into an agitator typically of mechanical type, such as a planetary ball mill system, in which the rotation of appropriately filled jars causes the Mg and B powders to knock into each other, against the inner walls and against some metal balls contained therein.
The step of mixing of the powders is very delicate not only, as mentioned, for the need to obtain a homogenous mixture free from undesired contaminants, but also because all the steps in which the operator must handle the powders must be carried out in closed environments, to operate inside which the operators must insert their hands in specific fixed gripping gloves through the security glass which separates the operator from the working environment.
Consequently, the step of mixing in the known type processes requires a manual intervention by the operator which implies a given degree of difficulty and discomfort for the operator.
After having completed the mixing, the operator fills a tube made of metal or appropriate alloy with the mixed powders (billet). Such a billet is thus mechanically deformed, typically by drawing and/or rolling processes as needed, to produce a superconductor wire of smaller diameter and greater length than the initial one. Finally, the wire is subjected to a thermal treatment so as to trigger the reaction between the boron and the magnesium and thus make the magnesium-diboride- based compound inside the metal or alloy sheath which constituted the initial containing tube.
Disadvantageously, the production of MgB2 superconductors starting from mixing powders implies a substantial risk of lack of uniformity inside the material. In practice, in case of imperfect mixing, a prevalence of boron or of magnesium powder may be created in some zones. Consequently, such a material in excess does not react and remains as impurity in the superconductor. Furthermore, this creates lack of uniformity in the distribution of the MgB2, which reflects on a lack of uniformity and lowers the mechanical properties of the wire itself. Additionally, since the mass density of the MgB2 compound is significantly higher than the mass densities of the boron and magnesium elements in mixed state, the aforesaid thermal reaction causes the formation of a spongiform MgB2 structure, in which the superconductor particles are surrounded by holes, which may result as interruptions of continuity of the superconductor structure, thus significantly limiting the electrical properties.
Summary
In this context, the technical task underlying the present invention is to suggest a method for the production of superconductors which overcomes the drawbacks of the prior art mentioned above.
In particular, it is the object of the present invention to make available a method for the production of superconductors capable of guaranteeing better mechanical and electrical properties to the product.
It is a further object of the present invention to make available a method for the production of superconductors capable of reducing the product anisotropies to the minimum.
The technical task and the specified objects are substantially achieved by a method for the production of superconductors comprising the technical features illustrated in one or more of the appended claims. In particular, the method for the production of superconductors according to the present invention comprises a step of preparing a sheet of a first material. Such a first material is preferably magnesium, either pure or possibly with the addition of impurities chosen and controlled to increase the transporting properties or the mechanical properties. The sheet has a longitudinal development axis.
A predetermined amount of powder of a second material is thus dosed. Such a second material is preferably boron, either pure or possibly with the addition of impurities chosen and controlled to increase the transporting properties or the mechanical properties. Such a powder is spread on the sheet according to a predetermined dosing so as to define a layer of second material. In particular, the dosing is performed according to a stoichiometric ratio Mg:B of 1 :2, except for variations which take dopants or additives into account.
The sheet is thus wrapped along the longitudinal axis to obtain a blank. Optionally, such a step of wrapping may comprise the sub-step of preparing a support having a prevalent development axis parallel to the longitudinal development axis.
The sheet is thus wrapped to obtain a blank. Such a blank is then processed by drawing and rolling to turn it into a wire.
The wire is then thermally treated to obtain the formation of the MgB2 superconductor by means of the reaction between the boron powders and the magnesium sheet.
The superconductor resulting from the method according to the present invention will have an internal spiral structure. Such a structures is basically more uniform than that known until now in the prior art, and also has considerably improved mechanical properties, because the voids present are uniformly distributed along the length and the spacing between the planes of the spiral allows movements of the MgB2 planes without causing the creation of fractures caused by the bending of the wire.
Brief description of the figures
Further features and advantages of the present invention will be more apparent in the following indicative and consequently non-limitative description of a preferred, but not exclusive embodiment of a method for the production of superconductors, as shown on the accompanying drawings, in which: - figure 1 diagrammatically shows a first step of the method for the production of superconductors according to the present invention;
- figure 2 diagrammatically shows a second step of the method for the production of superconductors according to the present invention; and
- figure 3 diagrammatically shows a third step of the method for the production of superconductors according to the present invention.
Detailed description of the invention
A method for the production of superconductors according to the present invention will now be described with reference to the accompanying figures.
In particular, figure 1 shows a step of preparing a sheet 1 of a first material. Such a first material is preferably magnesium. The sheet has a longitudinal development axis "A". More in particular, the sheet 1 has a rectangular shape. In different embodiments of the invention, the development axis "A" may be defined in parallel to the either longer side or shorter side of the sheet 1 .
A predetermined amount of powder of a second material is thus dosed. Such a second material is preferably boron. Such a powder is spread on the sheet 1 according to a predetermined dosing to define a layer 2 of second material. Dosing occurs in particular according to a stoichiometric ratio between the first and the second material 1 :2.
In further detail, the distribution of the second material on the sheet 1 may be carried out homogeneously, e.g. by roughly applying the powder and then distributing it with a predetermined spacer. In order to make such a composition more stable, a pressure can be applied (e.g. by means of a metal surface) on the layer 2 so as to compact the powder and make it adhere to the surface of the sheet 1 in a preliminary manner so as to wrap it. In an alternative embodiment (not shown), a further sheet of material is added and pressed on the layer 2 to define a containment for the powders.
Alternatively, the powders of second material may be mixed with an appropriate substance which is easily evaporable but not water-based, such as, for example ultra-pure isopropyl alcohol, which may help to spread the powders of second material uniformly on the sheet 1 . The added liquid may be subsequently removed by evaporation either at ambient temperature or at higher temperature, possibly in vacuum conditions to accelerate the process. Advantageously, in this manner, the uniform spreading of the layer 2 is facilitated and the required position and size of the layer 2 is maintained.
With reference to figure 2, the sheet 1 covered with the layer of powder 2 is wrapped along the longitudinal development axis "A" to obtain a blank 3. Such a step of wrapping may comprise the sub-step of preparing a support 4 having a prevalent development axis "B" parallel to the longitudinal development axis "A". The sheet 1 may be wound on such a support 4. In particular, the support is a wire or a tube. In particular, such a support 4 may also have a function of improving the mechanical and/or electrical properties of the wire once completed.
The method comprises the further step of inserting the blank 3 in a casing 7. In particular, such a casing 7 comprises a tube, preferably cylindrical, having a cavity 7a adapted to house the blank. The casing 7 is preferably made of steel, or of various alloys, in particular nickel-based. It is worth noting that, according to with the present invention, the step of inserting the blank 3 inside the casing 7 is carried out before the step of thermal treating.
Subsequently, the blank 3 is subjected to drawing to obtain a wire 5. Such a wire 5 may be cut, in turn, into a plurality of pieces of predetermined length. The wires 5 may thus be stacked again, according to a predetermined mode, and re- introduced into a further casing (not shown). The assembly may be processed again in manner similar to the wire 5, so as to obtain a wire comprising a plurality of MgB2 cores, named "multifilamentary" wire in the technical jargon of the sector. The blank 3 is thus thermally treated to obtain a wire 5 of superconductor 6. In particular, such a superconductor is magnesium diboride. In further detail, the thermal treatment cycle comprises at least one step in which the wire 5 is taken to a temperature higher than the melting temperature of magnesium. In this manner, the sheet 1 passes either partially or totally to the liquid state and, by reacting with the boron powder, produces the superconductor 6 uniformly along the entire wire 5.
The method further comprises a step of pressurizing of the blank 3, during the thermal treatment or subsequently thereafter. In particular, a mechanical or pneumatic pressure is exerted externally to the wire 5 on the surface thereof so as to compress the external diameter. Advantageously, this allows to either reduce or eliminate possible areas devoid of superconductor inside the wire 5.
Optionally, a plurality of pieces of a plurality of pieces of blank 3 can be inserted inside a further casing (not shown). Such a casing is thus pressurized and thermally treated. In particular, the further casing filled with the pieces of blank 3 may be processed in manner similar to the blank 3 itself, so as to obtain a wire comprising a plurality of MgB2 cores.

Claims

1 . Method for the production of superconductors, comprising the steps of preparing a sheet (1 ) of a first material having a longitudinal development axis (A); dosing a predetermined amount of powder of a second material; uniformly spreading said powder on said sheet (1 ) to define a layer (2) of said second material; wrapping said sheet along said longitudinal axis (A) to obtain a blank (3); thermally treating said blank (3) to obtain a billet of superconductor (6).
2. Method according to the preceding claim, characterized in that said first material is magnesium.
3. Method according to any one of the preceding claims, characterized in that said second material is boron.
4. Method according to any one of the preceding claims, characterized in that said measuring step is carried out according to a stoichiometric ratio 2:1 .
5. Method according to any one of the preceding claims, characterized in that said measuring step comprises a step of adding chemical additives to change the transport properties and/or mechanical properties of said superconductor (6).
6. Method according to any one of the preceding claims, characterized in that it comprises the step of adding a liquid or semi-liquid organic substance to said powder of said second material, said organic substance being evaporable after spreading said powder on said sheet (1 ).
7. Method according to any one of the preceding claims, characterized in that said wrapping step comprises the sub-steps of preparation of a support (4) having a prevalent development axis (B) parallel to said longitudinal development axis (A); wrapping said sheet (1 ) on said support (4).
8. Method according to the preceding claim, wherein said support (4) is a wire.
9. Method according to claim 7, wherein said support (4) is a tube.
10. Method according to any one of the preceding claims, characterized in that it further comprises the insertion step of said blank (3) in a casing (7).
1 1 . Method according to the preceding claim, wherein said insertion is carried out before said heat treatment step.
12. Method according to any one of the preceding claims, characterized in that it comprises a step of pressurization of said blank (3), said pressurization step being carried out during or after said heat treatment step.
13. Method according to any one of the preceding claims, characterized in that it comprises the further steps of inserting plurality of pieces of said blank (3) inside an additional casing; pressurizing said further casing; thermally treating said further casing to obtain a wire comprising a plurality of MgB2 cores.
14. Plant configured to carry out a method for the production of superconductors according to any one of the preceding claims.
PCT/IB2016/050425 2015-01-28 2016-01-28 Method for the production of superconductors WO2016120816A1 (en)

Applications Claiming Priority (2)

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ITMI2015A000105 2015-01-28
ITMI20150105 2015-01-28

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090258787A1 (en) * 2008-03-30 2009-10-15 Hills, Inc. Superconducting Wires and Cables and Methods for Producing Superconducting Wires and Cables
US20120100203A1 (en) * 2009-05-27 2012-04-26 Board Of Regents, The University Of Texas System Fabrication of Biscrolled Fiber Using Carbon Nanotube Sheet
US20130123112A1 (en) * 2010-07-21 2013-05-16 Tabea Arndt Method and arrangement for producing superconducting layers on substrates

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090258787A1 (en) * 2008-03-30 2009-10-15 Hills, Inc. Superconducting Wires and Cables and Methods for Producing Superconducting Wires and Cables
US20120100203A1 (en) * 2009-05-27 2012-04-26 Board Of Regents, The University Of Texas System Fabrication of Biscrolled Fiber Using Carbon Nanotube Sheet
US20130123112A1 (en) * 2010-07-21 2013-05-16 Tabea Arndt Method and arrangement for producing superconducting layers on substrates

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