EP2545563A1 - Matériaux magnétocaloriques - Google Patents

Matériaux magnétocaloriques

Info

Publication number
EP2545563A1
EP2545563A1 EP11752934A EP11752934A EP2545563A1 EP 2545563 A1 EP2545563 A1 EP 2545563A1 EP 11752934 A EP11752934 A EP 11752934A EP 11752934 A EP11752934 A EP 11752934A EP 2545563 A1 EP2545563 A1 EP 2545563A1
Authority
EP
European Patent Office
Prior art keywords
magnetocaloric
solid
cooling
stage
materials
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.)
Granted
Application number
EP11752934A
Other languages
German (de)
English (en)
Other versions
EP2545563A4 (fr
EP2545563B1 (fr
Inventor
Ekkehard BRÜCK
Zhiqiang OU
Lian Zhang
Caron Luana
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to EP11752934.7A priority Critical patent/EP2545563B1/fr
Publication of EP2545563A1 publication Critical patent/EP2545563A1/fr
Publication of EP2545563A4 publication Critical patent/EP2545563A4/fr
Application granted granted Critical
Publication of EP2545563B1 publication Critical patent/EP2545563B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/012—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials adapted for magnetic entropy change by magnetocaloric effect, e.g. used as magnetic refrigerating material
    • H01F1/015—Metals or alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0207—Using a mixture of prealloyed powders or a master alloy
    • C22C33/0214—Using a mixture of prealloyed powders or a master alloy comprising P or a phosphorus compound
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24V—COLLECTION, PRODUCTION OR USE OF HEAT NOT OTHERWISE PROVIDED FOR
    • F24V99/00—Subject matter not provided for in other main groups of this subclass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

Definitions

  • the invention relates to polycrystalline magnetocaloric materials, to processes for their production and to their use in coolers, heat exchangers or generators, in particular in refrigerators.
  • Thermomagnetic materials also referred to as magnetocaloric materials, can be used for cooling, for example in refrigerators or air conditioning units, in heat pumps or for direct generation of power from heat without intermediate connection of a conversion to mechanical energy.
  • Magnetic cooling techniques are based on the magnetocaloric effect (MCE) and may constitute an alternative to the known vapor circulation cooling methods.
  • MCE magnetocaloric effect
  • the alignment of randomly aligned magnetic moments by an external magnetic field leads to heating of the material.
  • This heat can be removed from the MCE material to the surrounding atmosphere by a heat transfer.
  • the magnetic field is then switched off or removed, the magnetic moments revert back to a random arrangement, which leads to cooling of the material below ambient temperature. This effect can be exploited for cooling purposes, but also for heating.
  • a heat transfer medium such as water is used for heat removal from the magnetocaloric material.
  • thermomagnetic generators are likewise based on the magnetocaloric effect.
  • a material which exhibits a magnetocaloric effect a small change in temperature can lead to a big change in magnetization. Magnetized by an external magnetic field, when the material is heated, a big change in the induction flow through a coil and thus an electromotive force are generated. Cooling the material below the critical temperature leads again to the occurrence of an electromotive force. This effect can be exploited for conversion of heat to electrical energy.
  • the magnetocaloric generation of electrical energy is associated with magnetic heating and cooling.
  • the process for energy generation was described as pyromagnetic energy generation.
  • these magnetocaloric devices can have a significantly higher energy efficiency.
  • Kirol described numerous possible applications and conducted thermodynamic analyses thereof.
  • gadolinium was considered to be a potential material for applications close to room temperature.
  • a pyromagnetoelectric generator is described, for example, by N. Tesla in US 428,057.
  • the magnetic properties of iron or other magnetic substances can be destroyed partially or entirely or can disappear as a result of heating to a particular temperature. In the course of cooling, the magnetic properties are re-established and return to the starting state. This effect can be exploited to generate electrical power.
  • an electrical conductor is exposed to a varying magnetic field, the changes in the magnetic field lead to the induction of an electrical current in the conductor.
  • the magnetic material is surrounded by a coil and is then heated in a permanent magnetic field and then cooled, an electrical current is induced in the coil in the course of heating and cooling in each case. This allows thermal energy to be converted to electrical energy, without an intermediate conversion to mechanical work.
  • iron as the magnetic substance, is heated by means of an oven or a closed fireplace and then cooled again.
  • thermomagnetic or magnetocaloric applications the material should permit efficient heat exchange in order to be able to achieve high efficiencies. Both in the course of cooling and in the course of power generation, the thermomagnetic material is used in a heat exchanger.
  • x preferably has a minimum value of 0.28, more preferably of 0.3.
  • the maximum value of x is preferably 0.34, in particular 0.33. More preferably 0.28 ⁇ x ⁇ 0.34, in particular 0.30 ⁇ x ⁇ 0.33.
  • y preferably has a minimum value of 0.4.
  • the maximum value of y is preferably 0.6, more preferably 0.44. More preferably 0.4 ⁇ y ⁇ 0.6, in particular 0.4 ⁇ y ⁇ 0.44.
  • z may differ from 0 by small values.
  • -0.05 ⁇ z ⁇ 0.05, in particular -0.02 ⁇ z ⁇ 0.02, especially z 0.
  • the inventive magnetocaloric materials preferably have a hexagonal structure of the Fe 2 P type.
  • the inventive materials allow a working temperature in application in the range from 0°C to + 150°C.
  • the magnetocaloric effect of the inventive materials is comparable to the magnetocaloric effect of what are known as giant magnetocaloric materials such as MnFeP x Asi -x ,Gd 5 (Si, Ge) 4 or La(Fe, Si) 13 -
  • the thermal hysteresis determined in a magnetic field of 1 T with a sweep rate of c/min, is preferably ⁇ 5°C, more preferably ⁇ 2°C, due to the balanced Mn/Fe and P Si ratios.
  • the inventive materials additionally have the advantage that they are formed from elements which are available in large amounts and are generally classified as nontoxic.
  • the thermomagnetic materials used in accordance with the invention can be produced in any suitable manner.
  • the inventive magnetocaloric materials can be produced by solid phase conversion or liquid phase conversion of the starting elements or starting alloys for the material, subsequently cooling, then pressing, sintering and heat treating under inert gas atmosphere and subsequently cooling to room temperature, or by melt spinning of a melt of the starting elements or starting alloys.
  • thermomagnetic materials are produced, for example, by solid phase reaction of the starting elements or starting alloys for the material in a ball mill, subsequent pressing, sintering and heat treatment under inert gas atmosphere and subsequent cooling, for example slow cooling, to room temperature.
  • a process is described, for example, in J. Appl. Phys. 99, 2006, 08Q107.
  • suitable amounts of Mn, Fe, P and Si in element form or in the form of preliminary alloys such as Mn 2 P or Fe 2 P can be ground in a ball mill.
  • the powders are pressed and sintered at temperatures in the range from 900 to 1300°C, preferably of about 1 100°C, for a suitable time, preferably 1 to 5 hours, especially about 2 hours, and then heat treated at temperatures in the range from 700 to 1000°C, preferably about 850°C, for suitable periods, for example 1 to 100 hours, more preferably 10 to 30 hours, especially about 20 hours, under a protective gas atmosphere.
  • the element powders or preliminary alloy powders can be melted together in an induction oven. It is then possible in turn to perform a heat treatment as specified above.
  • thermomagnetic materials comprising the following steps: converting chemical elements and/or alloys in a stoichiometry which corresponds to the magnetocaloric material in the solid and/or liquid phase, optionally converting the reaction product from stage a) to a solid, sintering and/or heat treating the solid from stage a) or b), quenching the sintered and/or heat treated solid from stage c) at a cooling rate of at least 100 K/s.
  • the thermal hysteresis can be reduced significantly and a large magnetocaloric effect can be achieved when the magnetocaloric materials are not cooled slowing to ambient temperature after the sintering and/or heat treatment, but rather are quenched at a high cooling rate.
  • This cooling rate is at least 100 K/s.
  • the cooling rate is preferably from 100 to 10 000 K/s, more preferably from 200 to 1300 K/s. Especially preferred cooling rates are from 300 to 1000 K/s.
  • the quenching can be achieved by any suitable cooling processes, for example by quenching the solid with water or aqueous liquids, for example cooled water or ice/water mixtures.
  • the solids can, for example, be allowed to fall into ice-cooled water. It is also possible to quench the solids with subcooled gases such as liquid nitrogen. Further processes for quenching are known to those skilled in the art. What is advantageous here is controlled and rapid cooling.
  • the rest of the production of the magnetocaloric/thermomagnetic materials is less critical, provided that the last step comprises the quenching of the sintered and/or heat treated solid at the inventive cooling rate.
  • the process may be applied to the production of any suitable thermomagnetic materials, as described above.
  • step (a) of the process the elements and/or alloys which are present in the later thermomagnetic material are converted in a stoichiometry which corresponds to the thermomagnetic material in the solid or liquid phase.
  • a reaction is known in principle; cf. the documents cited above.
  • powders of the individual elements or powders of alloys of two or more of the individual elements which are present in the later thermomagnetic material are mixed in pulverulent form in suitable proportions by weight. If necessary, the mixture can additionally be ground in order to obtain a microcrystalline powder mixture.
  • This powder mixture is preferably heated in a ball mill, which leads to further comminution and also good mixing, and to a solid phase reaction in the powder mixture.
  • the individual elements are mixed as a powder in the selected stoichiometry and then melted.
  • the combined heating in a closed vessel allows the fixing of volatile elements and control of the stoichiometry. Specifically in the case of use of phosphorus, this would evaporate easily in an open system.
  • the reaction is followed by sintering and/or heat treatment of the solid, for which one or more intermediate steps can be provided.
  • the solid obtained in stage a) can be subjected to shaping before it is sintered and/or heat treated.
  • melt-spinning processes are known per se and are described, for example, in Rare Metals, Vol. 25, October 2006, pages 544 to 549, and also in WO 2004/068512 and WO 2009/133049.
  • the composition obtained in stage a) is melted and sprayed onto a rotating cold metal roller.
  • This spraying can be achieved by means of elevated pressure upstream of the spray nozzle or reduced pressure downstream of the spray nozzle.
  • a rotating copper drum or roller is used, which can additionally optionally be cooled.
  • the copper drum preferably rotates at a surface speed of from 10 to 40 m/s, especially from 20 to 30 m/s.
  • the liquid composition is cooled at a rate of preferably from 10 2 to 10 7 K/s, more preferably at a rate of at least 10 4 K/s, especially with a rate of from 0.5 to 2 x 10 6 K/s.
  • the melt-spinning like the reaction in stage a) too, can be performed under reduced pressure or under an inert gas atmosphere.
  • melt-spinning achieves a high processing rate, since the subsequent sintering and heat treatment can be shortened. Specifically on the industrial scale, the production of the thermomagnetic materials thus becomes significantly more economically viable. Spray-drying also leads to a high processing rate. Particular preference is given to performing melt spinning.
  • spray cooling can be carried out, in which a melt of the composition from stage a) is sprayed into a spray tower.
  • the spray tower may, for example, additionally be cooled.
  • cooling rates in the range from 10 3 to 10 5 K/s, especially about 10 4 K/s, are frequently achieved.
  • the sintering and/or heat treatment of the solid is effected in stage c) as described above.
  • the period for sintering or heat treatment can be shortened significantly, for example to periods of from 5 minutes to 5 hours, preferably from 10 minutes to 1 hour. Compared to the otherwise customary values of 10 hours for sintering and 50 hours for heat treatment, this results in a major time advantage.
  • the sintering/heat treatment results in partial melting of the particle boundaries, such that the material is compacted further.
  • stage b) The melting and rapid cooling in stage b) thus allows the duration of stage c) to be reduced considerably. This also allows continuous production of the thermomagnetic materials.
  • inventive magnetocaloric materials can be used in any suitable applications.
  • they are used in coolers, heat exchangers or generators. Particular preference is given to use in refrigerators.
  • the invention is illustrated in detail by examples.
  • the magnetic properties of the samples thus prepared were determined in a Quantum Design MPMSXL SQUID magnetometer.
  • Figure 1 shows the temperature dependence of the magnetization M(Am 2 kg "1 ), determined with a sweep rate of 1 K/min in a magnetic field of 1 T.
  • the temperature dependence between the heating and cooling curves at the transition shows the thermal hysteresis of the first-order magnetic transition for these samples. The value depends on the particular sample, but is always less than 2 K in the samples studied.
  • the significant change in magnetization in the region of about 70 Am 2 kg "1 as a result of the sharp magnetic transition shows a large magnetocaloric effect.
  • Figure 2 shows the change in magnetic entropy -AS n (J/kg K) as a function of temperature for these samples.
  • the change in magnetic entropy was derived from the magnetic isotherms, measured at different temperatures close to the transition, using the Maxwell equation.
  • the values obtained for the change in magnetic entropy are comparable to corresponding values for the so-called GMCEs (giant magnetocaloric effect materials).
  • the unfilled symbols relate to a field change of 0-1 T.
  • the filled symbols represent a field change for 0-2 T.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Power Engineering (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • General Engineering & Computer Science (AREA)
  • Hard Magnetic Materials (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)
  • Compounds Of Iron (AREA)
  • Manufacturing Cores, Coils, And Magnets (AREA)
  • Heat Treatment Of Articles (AREA)

Abstract

La présente invention concerne des matériaux magnétocaloriques de formule générale (MnxFe1-x)2+zP1-ySiy dans laquelle 0,20≤x ≤0,40 0,4≤y ≤0,8 -0,1 ≤z ≤0,1.
EP11752934.7A 2010-03-11 2011-03-09 Matériau magnétocalorique et procede de sa production Not-in-force EP2545563B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11752934.7A EP2545563B1 (fr) 2010-03-11 2011-03-09 Matériau magnétocalorique et procede de sa production

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP10156184 2010-03-11
PCT/IB2011/050982 WO2011111004A1 (fr) 2010-03-11 2011-03-09 Matériaux magnétocaloriques
EP11752934.7A EP2545563B1 (fr) 2010-03-11 2011-03-09 Matériau magnétocalorique et procede de sa production

Publications (3)

Publication Number Publication Date
EP2545563A1 true EP2545563A1 (fr) 2013-01-16
EP2545563A4 EP2545563A4 (fr) 2016-02-17
EP2545563B1 EP2545563B1 (fr) 2017-05-31

Family

ID=44562927

Family Applications (1)

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EP11752934.7A Not-in-force EP2545563B1 (fr) 2010-03-11 2011-03-09 Matériau magnétocalorique et procede de sa production

Country Status (11)

Country Link
EP (1) EP2545563B1 (fr)
JP (1) JP5809646B2 (fr)
KR (1) KR101848520B1 (fr)
CN (1) CN102792393B (fr)
AU (1) AU2011225713A1 (fr)
BR (1) BR112012021783A2 (fr)
CA (1) CA2789797A1 (fr)
NZ (1) NZ601798A (fr)
RU (1) RU2012143308A (fr)
TW (1) TW201140625A (fr)
WO (1) WO2011111004A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019071034A1 (fr) * 2017-10-04 2019-04-11 Calagen, Inc. Génération de champ magnétique avec refroidissement magnéto-calorique
US11223301B2 (en) 2019-08-20 2022-01-11 Calagen, LLC Circuit for producing electrical energy

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CN102513536A (zh) * 2011-12-28 2012-06-27 北京工业大学 一种磁制冷材料的制备工艺
US9245673B2 (en) 2013-01-24 2016-01-26 Basf Se Performance improvement of magnetocaloric cascades through optimized material arrangement
KR20160003693A (ko) 2013-05-08 2016-01-11 바스프 에스이 자기 냉각 장치를 위한 회전 자기 차폐 시스템의 용도
US9887027B2 (en) 2013-09-27 2018-02-06 Basf Se Corrosion inhibitors for Fe2P structure magnetocaloric materials in water
KR101575861B1 (ko) 2014-02-13 2015-12-10 충북대학교 산학협력단 자기 열량 금속 산화물 및 이의 제조방법
WO2016104739A1 (fr) * 2014-12-26 2016-06-30 大電株式会社 Procédé de production d'un matériau de réfrigération magnétique
KR102563429B1 (ko) * 2015-10-30 2023-08-04 테크니쉐 유니버시테이트 델프트 망간, 철, 규소, 인, 및 질소를 포함하는 자기열량 물질
US11410803B2 (en) * 2016-06-10 2022-08-09 Technische Universiteit Delft Magnetocaloric materials comprising manganese, iron, silicon, phosphorus and carbon
US11056265B2 (en) 2017-10-04 2021-07-06 Calagen, Inc. Magnetic field generation with thermovoltaic cooling
KR102069770B1 (ko) 2018-06-07 2020-01-23 한국생산기술연구원 자기열량합금 및 이의 제조 방법
US11996790B2 (en) 2019-08-20 2024-05-28 Calagen, Inc. Producing electrical energy using an etalon
US11942879B2 (en) 2019-08-20 2024-03-26 Calagen, Inc. Cooling module using electrical pulses
KR102665067B1 (ko) * 2020-01-28 2024-05-13 현대자동차주식회사 Al을 포함하는 Mn계 자기열량 물질
KR102651747B1 (ko) 2021-11-30 2024-03-28 한국재료연구원 자기열량합금 및 이의 제조방법
CN114540657B (zh) * 2022-03-24 2022-11-25 中南大学 一种具有宽频电磁屏蔽的稀土铜合金材料及其制备方法
KR102589531B1 (ko) 2022-04-20 2023-10-16 한국재료연구원 자기열량합금 및 이의 제조방법

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019071034A1 (fr) * 2017-10-04 2019-04-11 Calagen, Inc. Génération de champ magnétique avec refroidissement magnéto-calorique
US11223301B2 (en) 2019-08-20 2022-01-11 Calagen, LLC Circuit for producing electrical energy

Also Published As

Publication number Publication date
JP2013527308A (ja) 2013-06-27
JP5809646B2 (ja) 2015-11-11
AU2011225713A1 (en) 2012-08-23
CN102792393A (zh) 2012-11-21
CA2789797A1 (fr) 2011-09-15
BR112012021783A2 (pt) 2016-05-17
RU2012143308A (ru) 2014-04-20
KR20130051440A (ko) 2013-05-20
TW201140625A (en) 2011-11-16
WO2011111004A1 (fr) 2011-09-15
NZ601798A (en) 2014-01-31
CN102792393B (zh) 2016-06-15
KR101848520B1 (ko) 2018-04-12
EP2545563A4 (fr) 2016-02-17
EP2545563B1 (fr) 2017-05-31

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