EP2422347A1 - Magnetisches legierungsmaterial und verfahren zu seiner herstellung - Google Patents
Magnetisches legierungsmaterial und verfahren zu seiner herstellungInfo
- Publication number
- EP2422347A1 EP2422347A1 EP10718525A EP10718525A EP2422347A1 EP 2422347 A1 EP2422347 A1 EP 2422347A1 EP 10718525 A EP10718525 A EP 10718525A EP 10718525 A EP10718525 A EP 10718525A EP 2422347 A1 EP2422347 A1 EP 2422347A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alloy material
- magnetic alloy
- magnetic
- particles
- matrix
- 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
Links
- 239000000956 alloy Substances 0.000 title claims abstract description 94
- 229910001004 magnetic alloy Inorganic materials 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 9
- 230000008569 process Effects 0.000 title claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 43
- 239000002245 particle Substances 0.000 claims abstract description 34
- 239000011159 matrix material Substances 0.000 claims abstract description 32
- 230000000694 effects Effects 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052733 gallium Inorganic materials 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 238000005056 compaction Methods 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 238000005187 foaming Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 230000005291 magnetic effect Effects 0.000 abstract description 37
- 238000001816 cooling Methods 0.000 abstract description 21
- 230000008859 change Effects 0.000 description 35
- 229910045601 alloy Inorganic materials 0.000 description 7
- 108010053481 Antifreeze Proteins Proteins 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000011343 solid material Substances 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000005275 alloying Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910000859 α-Fe Inorganic materials 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 210000000497 foam cell Anatomy 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 238000005382 thermal cycling Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017034 MnSn Inorganic materials 0.000 description 1
- 238000010314 arc-melting process Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
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
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/14—Making alloys containing metallic or non-metallic fibres or filaments by powder metallurgy, i.e. by processing mixtures of metal powder and fibres or filaments
-
- 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
- H01F1/017—Compounds
Definitions
- the invention relates to the field of materials science and material physics and relates to a magnetic alloying material, which can be used, for example, as a magnetic cooling material (magnetocaloric material) for cooling purposes or for power generation purposes, and a method for its preparation.
- a magnetic alloying material which can be used, for example, as a magnetic cooling material (magnetocaloric material) for cooling purposes or for power generation purposes, and a method for its preparation.
- Magnetic cooling by magnetic alloy materials provides an environmentally friendly, energy and cost effective alternative to conventional gas compression refrigeration.
- MCE magnetocaloric effect
- Magnetic materials with a crystal structure of NaZni 3 type show a particularly large MCE, which is caused by a thermally and field-induced phase transition from the paramagnetic to the ferromagnetic state near the Curie temperature T 0 of the material.
- Magnetic alloy materials of the NaZrH 3 crystal structure are known and could be used as magnetic cooling materials.
- the composition of such materials may be represented by the formula R (Ti -a M a) i3Hd be given, with rare-earth elements for R, or a combination rare earth elements for T is Fe or a combination of Fe and Co and M Al, Si, Ga, or Ge, or Combinations thereof are used.
- R Ti -a M a
- i3Hd rare-earth elements
- rare earth elements for T is Fe or a combination of Fe and Co and M Al, Si, Ga, or Ge, or Combinations thereof are used.
- 0.05 ⁇ a ⁇ 0.2 and for d, 0 ⁇ d ⁇ J3.0 Such materials have very good magneto
- such magnetic alloys are produced by means of an arc or high-frequency melting process and then heat-treated for about 168 hours at about 1050 ° C. under vacuum (DE 103 38 467 A1). It is also possible to melt the alloying elements at 1200 to 1800 0 C, then cool with cooling rates of 10 2 to 10 6 ° C / s (rapidly solidify) and then thermally treat the rapidly solidified alloy [US 2006/0076084 A1; A. Yan, K.-H. Müller, O. Gutées, J. Appl. Phys. 97, 036102 (2005); XB Liu, Z. Altounian, GH Tu, J. Phys .: Condens. Matter 16, 8043 (2004)].
- a number of magnetic alloys such as Gd 5 Si 2 Ge 2 , MnAs, Mni -x Fe x As, Ni 2 MnSn and (Mn 1 Fe) 2 (P 1 As) are known, which show in part a particularly large MCE by causing a thermally and / or field-induced magnetic phase transition near the Curie temperature T 0 and / or near a structural phase transition
- a significant disadvantage of these alloys is known to be the occurrence of volume changes due to isotropic or anisotropic expansion of the crystal lattice during the magnetic or structural phase transition, especially for the alloys showing a first-order phase transition [A. Fujita et al., Phys. Rev B 65, 014410 (2001); H. Yabuta et al., J. Phys. Soc. Japan, 75, 113707 (2006)].
- These changes in volume can result in significantly reduced mechanical integrity and thus severely limiting conditions of use.
- the object of the present invention is to provide a magnetic alloying material which has improved mechanical properties with comparable magnetic and / or magnetocaloric properties over the prior art materials, and an indication of an effective method for producing the magnetic alloy material.
- the magnetic alloy material of the present invention which exhibits a magnetocaloric effect and which has a foam-like structure with an open porosity of 1% to 50% and / or a closed porosity of at least 1%, or wherein the particles of the magnetic alloy material in a matrix material with a higher ductility than the magnetic alloy material are embedded.
- > 35% by volume of the magnetic alloy material has a NaZni 3 type crystal structure, more preferably at least 50% by volume, more preferably 80-90% by volume, of the magnetic alloy material having a NaZni 3 crystal structure Type on.
- the magnetic alloy material has a composition according to the formula:
- R La or a combination of La with Ce, Pr, Nd, Sm, Gd, Tb,
- T at least one element selected from the group Sc, Ti, V, Cr,
- M Al, Si, P, Ga, Ge, In and / or Sn
- L H, B, C and / or N
- the conditions 2 ⁇ z ⁇ 15 at% and / or 3 5_y 1 16 and / or 0.3 ⁇ x ⁇ 9 are realized, wherein with varying proportion z and / or y and / or x the Curie temperature changes between 170 K and 400 K.
- the foam-like structure of the magnetic alloy material has an open porosity of 2 to 50% and / or a closed porosity of 2 to 50%.
- particles of the magnetic alloy material with a particle size of 10 nm to 1 mm are embedded in a matrix material.
- the matrix material with a higher ductility than the magnetic alloy material comprises at least one element of Al, Ag, Au, Bi, C, Co, Cu, Fe, Ga, Ni, Pb, Pd, Pt, Sn, Ti , Zn or combinations and / or reaction products thereof.
- a second material comprising at least one element of Al, Ag, Au, Bi, C, Co, Cu, Fe, Ga, Ni, Nb, Pb, Pd, Pt, Sn, Ta, Ti , V, Zn, Zr or combinations and / or reaction products also with the matrix material thereof is present.
- the matrix material has at least a 10% higher ductility than the magnetic alloy material.
- the particles of the magnetic alloy material are in the form of a band, a wire, a plate, a foil or a flake, a needle or in the form of powder particles.
- the magnetic alloy material is made into a foam-like structure by means of foaming or compaction, or particles of the magnetic alloy material are mixed with a matrix material having higher ductility than the magnetic alloy material and then heated to the extent that the matrix material forms the matrix around the particles of the magnetic alloy material.
- the compaction is carried out by hot or cold pressing.
- the foaming is carried out by applying a suspension with particles of the magnetic alloy material to a foam-like structure and drying, and subsequently burning out or pyrolyzing the foam-like structure.
- particles of the magnetic alloy material and of the matrix material are mixed and processed into a shaped body and subsequently heated to a temperature at which the matrix material at least softens and covers the particles of the magnetic alloy material substantially completely.
- the application temperature is adjusted by applying a vacuum.
- the magnetic alloy material has a foam-like structure or particles of the magnetic alloy material are embedded in a matrix material which has a higher ductility than the magnetic alloy material.
- Foam-like structure is to be understood in the context of this invention, a structure consisting of webs that limit foam cells. These foam cells are open.
- the web material consists essentially of the magnetic alloy material and has an open and / or closed porosity.
- the foam-like structure may also consist essentially of only magnetic alloy material with open and / or closed pores.
- the magnetic alloy material can be processed in the form of particles in a suspension to a shaped body or applied to a foam structure and processed after drying and a temperature increase to the magnetic alloy material.
- the particles of the magnetic alloy material may be present in the form of a band, a wire, a plate, a Fol ie or a flake, a needle or in the form of powder particles.
- the particles may also be in the form of a band, a wire, a plate, a foil or a flake, a needle or in the form of powder particles.
- the particle size can be from a few nanometers to ⁇ 100 microns.
- the particles of the magnetic alloying matehal can then be mixed with particles of the matrix material and processed into a shaped body. Subsequently, the molding is exposed to a temperature increase, wherein at least one such temperature must be achieved that the matrix material forms a matrix around the particles of the magnetic alloy material and substantially completely covers the surface of the particles as possible.
- the magnetic alloy material according to the invention exhibits a significantly higher mechanical strength, since the volume changes of the magnetic alloy material can be significantly better absorbed by the phase transition, which is present at a pore or the ductile matrix material, and thus counteract the cracking and possibly even the destruction of the molding and prevent it partially or completely.
- the solution according to the invention shows, in particular, improved results in the predominant use of magnetic alloy materials whose crystal structure is of the NaZni 3 type. These materials are known to have a large magnetocaloric effect and therefore can be used particularly advantageously.
- H, B, C and / or N are present in the alloy material.
- These elements are known to be incorporated into interstitial sites and in particular have an effect on the Curie temperature T 0 , which is known to be important for magnetic alloy materials and which is known to determine the temperature of use, as the Curie temperature is increased as the proportion of these elements, and in particular H, increases.
- T 0 Curie temperature
- an application temperature for the magnetic alloy material is adjustable within relatively wide limits.
- the effect of loading the magnetic alloy material with these elements is further improved by the solution according to the invention, since the increased brittleness of the magnetic alloy material resulting from the interaction is likewise absorbed by the foam-like structure or the matrix material become.
- the Curie or application temperature setting can be done for example by applying a vacuum during the temperature increase, which is also in the compaction by means of hot pressing or pressing at moderate temperatures feasible. About the height of the temperature or time, the application temperature can be adjusted.
- a specially selected coating method such as the electrochemical coating or electroless plating coating
- hydrogen can be introduced interstitially into the crystal lattice at the same time or substitute elements such as Co, Ni, Cu by diffusion processes Fe and thereby increase the Curie temperature T 0 .
- the hydrogen can be formed in a secondary reaction, such as released as a by-product of a cathodic electrode reaction or during the oxidation of the reducing agent.
- compaction e.g. By hot or cold pressing, or produced by foaming magnetic alloy material according to the invention has open and / or closed pores, with a particularly advantageous even a regular porosity can be adjusted.
- the pores are arranged directionally in the material, so that, for example, an effective flow through a (cooling) liquid can be achieved.
- a high specific surface area of the porous material is also very advantageous for effective heat exchange.
- the magnetic alloy material according to the invention has a density between 50% and 99% of the theoretically achievable density of the magnetic alloy material.
- this may also contain a further material or the further material may be formed by reactions of the matrix material or of another material.
- This further material can also be deposited on the surface of the particles of the magnetic alloy material.
- the magnetic entropy change remains virtually unchanged, ie the relative cooling power remains high.
- the adiabatic temperature change ⁇ T aC ⁇ decreases slightly.
- a high reproducibility after significantly more work cycles in comparison to a solid material is advantageous.
- a solid material with the composition LaFen, 6Sii, 4 is prepared by induction melting and subsequent heat treatment at 1050 0 C for 7 days.
- the resulting material consists of 97 wt .-% of the NaZni 3 -type phase and 3 wt .-% of ⁇ -Fe.
- the solid material with the composition LaFen, 6Sii, 4 shows at a magnetic field change of 2 Tesla a maximum entropy change ⁇ S ma ⁇ of 162 kJ / m 3 K at 194 K.
- the half-width is 8 K and the relative cooling capacity is 1, 5 MJ / m 3 .
- the entropy change and the relative cooling power remain unchanged after thermal cycling.
- the maximum adiabatic temperature change ⁇ T aC ⁇ max at a magnetic field change of 1.9 Tesla 7.3 K at 191 K when cooling from room temperature.
- the maximum adiabatic temperature change decreases with a magnetic field change from 1, 9 Tesla to 5.2 K at 1 94 K.
- the thermal hysteresis is 3 K and magnetic hysteresis up to 0.7 T.
- ⁇ T aC ⁇ max decreases to 6.7 K and 6.6 K during cooling from room temperature and to 5 K and 4.9 K during heating of 170 K to room temperature.
- the thermal hysteresis is 2.2 K and 2.1 K in the second and third thermal cycle.
- a porous, foam-like material from the pulverized solid material by hot pressing at press temperature of 600 - 1423 K, and pressing pressure of the order of ⁇ 10 2 - 10 3 MPa prepared.
- the resulting material consists of 91% by weight of the NaZni 3 -type phase and 9% by weight of ⁇ -Fe.
- the density of the pressed material is 70 to 90% of the theoretical density of the material which consists of 91% by weight of LaFen, 6 Sii, 4 and 9% by weight of ⁇ -Fe.
- 2 plates are cut from a cylindrical hot-pressed material having dimensions of 8 mm ⁇ 4 mm ⁇ 1 mm.
- the hot-pressed material with the composition LaFen, 6Sii, 4 shows a maximum entropy change ⁇ S ma ⁇ of 110 kJ / m 3 K at 194 K with a magnetic field change of 2 Tesla.
- the half-width is 10.5 K and the relative cooling capacity is 1, 3 MJ / m 3 .
- the entropy change and the relative cooling power remain unchanged after thermal cycling.
- the adiabatic temperature change ⁇ T aC ⁇ remains unchanged after the thermal and magnetic field alternating stress and is 4.3 K during cooling from room temperature and when heating 170 K to room temperature with a magnetic field change of 1.9 Tesla.
- the thermal hysteresis is less than 1 K, ie significantly lower compared to the solid material.
- the magnetic field dependence of the adiabatic temperature change is nearly hysteresis-free (less than 0.05 T).
- the mechanical integrity of the hot-pressed material remains after multiple thermal or field cycling cycles.
- an alloy having the composition LaFen , 6 Sii , 4 is produced by means of an arc melting process.
- the alloy is then rapidly solidified at the surface speed of the copper wheel of 30 m / s and then heat-treated at 1050 ° C. for 2 hours [J. Lyubina et al., J. Magn. Magn. Mater. 320, 2252 (2008)].
- the resulting material is in the form of a band with a thickness of 60 microns and consists of 90 wt .-% of the NaZni 3 - type phase and 10 wt .-% of ⁇ -Fe.
- a porous, foam-like material is produced by pressing at room temperature (cold pressing) and pressing pressure of 500 MPa.
- the dimensions of the pressed LaFen , 6 Sii , 4 alloy are 11 mm diameter x 1 mm height and the density is 85% of the theoretical density of the material.
- the cold-pressed LaFen, 6Sii, 4 alloy shows a maximum magnetic entropy change ⁇ S ma ⁇ of 145 kJ / m 3 K at 193 K and a magnetic field change of 2 Tesla.
- the half width is 8.3 K and the relative cooling capacity is 1.5 MJ / m 3 .
- the adiabatic temperature change ⁇ T aC ⁇ remains unchanged after the thermal and magnetic field alternating stress and is 4.3 K at 193 K when cooling from room temperature and when heating 170 K to room temperature with a magnetic field change of 1.9 Tesla. It is the thermal hysteresis less than 0.5 K.
- the magnetic field dependence of the adiabatic temperature change is almost hysteresis-free.
- This cold-pressed LaFen , 6 Sii , 4 -l_egtechnik is hydrogenated at 400 0 C in 0.5 MPa hydrogen gas.
- the hydrogen concentration of z 1.64 was measured by hot extraction. This corresponds to a composition of LaFen, 6Sii, 4 Hi 64 -
- the temperature at which the maximum of the entropy change or the adiabatic temperature change occurs shifts to 338 K.
- the adiabatic temperature change ⁇ T aC ⁇ remains unchanged after the thermal and magnetic field alternating stress and is 3.7 K during cooling from room temperature and when heating 170 K to room temperature with a magnetic field change of 1.9 Tesla.
- the temperature and magnetic field dependence of the adiabatic temperature change are almost hysteresis-free.
- the rapidly solidified and heat-treated ribbons are hydrogenated at 400 ° C. in 0.5 MPa hydrogen gas and then produced at a temperature of 650 K and a compression pressure of 500 MPa.
- the adiabatic temperature change ⁇ T aC ⁇ remains unchanged after the thermal and magnetic field alternating stress and is 3.6 K at 335 K with a magnetic field change of 1.9 Tesla.
- the temperature and magnetic field dependence of the adiabatic temperature change are almost hysteresis-free.
- the pressing at a temperature of 650 K under vacuum can be used at the same time for setting the Curie temperature or application temperature.
- the temperature at which the maximum of the entropy change or adiabatic temperature change occurs shifts to 300 K.
- the mechanical integrity of the hot or cold pressed material or material pressed at a temperature of 650 is maintained after multiple thermal or field cycling cycles.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Powder Metallurgy (AREA)
- Hard Magnetic Materials (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE200910002640 DE102009002640A1 (de) | 2009-04-24 | 2009-04-24 | Magnetisches Legierungsmaterial und Verfahren zu seiner Herstellung |
PCT/EP2010/055086 WO2010121977A1 (de) | 2009-04-24 | 2010-04-19 | Magnetisches legierungsmaterial und verfahren zu seiner herstellung |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2422347A1 true EP2422347A1 (de) | 2012-02-29 |
EP2422347B1 EP2422347B1 (de) | 2015-11-25 |
Family
ID=42224392
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP10718525.8A Not-in-force EP2422347B1 (de) | 2009-04-24 | 2010-04-19 | Magnetisches legierungsmaterial und verfahren zu seiner herstellung |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP2422347B1 (de) |
DE (1) | DE102009002640A1 (de) |
WO (1) | WO2010121977A1 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103388766A (zh) * | 2013-07-26 | 2013-11-13 | 宁波市爱使电器有限公司 | 一种高密封高散热的led灯 |
WO2017211921A1 (en) | 2016-06-10 | 2017-12-14 | Basf Se | Magnetocaloric materials comprising manganese, iron, silicon, phosphorus and carbon |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102113066B (zh) | 2009-05-06 | 2013-09-25 | 真空熔焠有限两合公司 | 磁热交换物体及制造磁热交换物体的方法 |
BR112015017315A2 (pt) * | 2013-01-24 | 2017-07-11 | Basf Se | cascata magnetocalórica, processo para produzir cascatas magnetocalóricas, uso de uma cascata magnetocalórica, e, sistemas de refrigeração, unidades de controle de clima e bombas de calor |
US9245673B2 (en) | 2013-01-24 | 2016-01-26 | Basf Se | Performance improvement of magnetocaloric cascades through optimized material arrangement |
DE102015119103A1 (de) * | 2015-11-06 | 2017-05-11 | Technische Universität Darmstadt | Verfahren zum Herstellen eines magnetokalorischen Verbundmaterials und Verbundmaterial mit einem magnetokalorischen Pulver |
DE102015222075A1 (de) * | 2015-11-10 | 2017-05-11 | Robert Bosch Gmbh | Verfahren zu Herstellung eines magnetischen Materials und elektrische Maschine |
DE102017102163B4 (de) | 2017-02-03 | 2020-10-01 | Leibniz-Institut Für Festkörper- Und Werkstoffforschung Dresden E.V. | Magnetokalorischer Wärmeübertrager und Verfahren zu seiner Herstellung |
DE102017128765A1 (de) * | 2017-12-04 | 2019-06-06 | Technische Universität Darmstadt | Verfahren zur Herstellung eines magnetokalorischen Verbundmaterials und ein entsprechender Wärmetauscher |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0217347B1 (de) * | 1985-09-30 | 1993-02-03 | Kabushiki Kaisha Toshiba | Verwendung polykristalliner magnetischer Substanzen zur magnetischen Abkühlung |
US6003320A (en) * | 1996-10-30 | 1999-12-21 | Kabushiki Kaisha Toshiba | Cold accumulating material for extremely low temperature cold, refrigerator using the same and heat shielding member |
JP4622179B2 (ja) * | 2001-07-16 | 2011-02-02 | 日立金属株式会社 | 磁気冷凍作業物質および蓄冷式熱交換器ならびに磁気冷凍装置 |
NL1018668C2 (nl) | 2001-07-31 | 2003-02-03 | Stichting Tech Wetenschapp | Materiaal geschikt voor magnetische koeling, werkwijze voor het bereiden ervan en toepassing van het materiaal. |
US6798117B2 (en) | 2002-07-10 | 2004-09-28 | Piezomotor Uppsala Ab | Fine control of electromechanical motors |
US7186303B2 (en) | 2002-08-21 | 2007-03-06 | Neomax Co., Ltd. | Magnetic alloy material and method of making the magnetic alloy material |
EP1554411B1 (de) | 2002-10-25 | 2013-05-08 | Showa Denko K.K. | Herstellungsverfahren einer seltenerdelement enthaltende legierung |
JP4240380B2 (ja) * | 2003-10-14 | 2009-03-18 | 日立金属株式会社 | 磁性材料の製造方法 |
US7578892B2 (en) | 2005-03-31 | 2009-08-25 | Hitachi Metals, Ltd. | Magnetic alloy material and method of making the magnetic alloy material |
JP2007031831A (ja) * | 2005-06-23 | 2007-02-08 | Sumitomo Metal Mining Co Ltd | 磁気冷凍用希土類−鉄−水素系合金粉末とその製造方法、および得られる押出構造体とその製造方法、並びにそれを用いた磁気冷凍システム |
DE102006046041A1 (de) * | 2006-09-28 | 2008-04-03 | Siemens Ag | Wärmeübertragungssystem für magnetokalorische Kühleinrichtungen und Herstellungsverfahren für einen dabei verwendeten Wärmeübertrager |
WO2008099234A1 (en) * | 2007-02-12 | 2008-08-21 | Vacuumschmelze Gmbh & Co. Kg. | Article for magnetic heat exchange and method of manufacturing the same |
GB2458039B (en) * | 2007-02-12 | 2012-07-25 | Vacuumschmelze Gmbh & Co Kg | Article for magnetic heat exchange and method of manufacturing the same |
CN101681707B (zh) * | 2007-12-27 | 2014-04-02 | 真空熔焠有限两合公司 | 具有磁热主动材料的复合物品及其制造方法 |
EP2109119A1 (de) * | 2008-04-07 | 2009-10-14 | Haute Ecole d'Ingénierie et de Gestion du Canton de Vaud (HEIG-VD) | Permeables magnetokalorisches Material und magnetischer Kühlschrank sowie Wärmepumpe oder Stromgenerator zur Verwendung dieses Materials |
-
2009
- 2009-04-24 DE DE200910002640 patent/DE102009002640A1/de not_active Withdrawn
-
2010
- 2010-04-19 EP EP10718525.8A patent/EP2422347B1/de not_active Not-in-force
- 2010-04-19 WO PCT/EP2010/055086 patent/WO2010121977A1/de active Application Filing
Non-Patent Citations (1)
Title |
---|
See references of WO2010121977A1 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103388766A (zh) * | 2013-07-26 | 2013-11-13 | 宁波市爱使电器有限公司 | 一种高密封高散热的led灯 |
CN103388766B (zh) * | 2013-07-26 | 2015-06-03 | 宁波市爱使电器有限公司 | 一种高密封高散热的led灯 |
WO2017211921A1 (en) | 2016-06-10 | 2017-12-14 | Basf Se | Magnetocaloric materials comprising manganese, iron, silicon, phosphorus and carbon |
US11410803B2 (en) | 2016-06-10 | 2022-08-09 | Technische Universiteit Delft | Magnetocaloric materials comprising manganese, iron, silicon, phosphorus and carbon |
Also Published As
Publication number | Publication date |
---|---|
DE102009002640A1 (de) | 2011-01-20 |
EP2422347B1 (de) | 2015-11-25 |
WO2010121977A1 (de) | 2010-10-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2422347B1 (de) | Magnetisches legierungsmaterial und verfahren zu seiner herstellung | |
DE102008054522B4 (de) | Verfahren zur Beschichtung der Oberflächeeines magnetischen Legierungsmaterials sowie ein solches Legierungsmaterial | |
DE112007003321B4 (de) | Gegenstand zum magnetischen Wärmeaustausch und Verfahren zu dessen Herstellung | |
DE3687680T2 (de) | Verwendung polykristalliner magnetischer substanzen zur magnetischen abkuehlung. | |
DE60221448T2 (de) | Seltenerdlegierungs Sinterformteil | |
DE10338467A1 (de) | Magnetisches Legierungsmaterial und Verfahren zur Herstellung des magnetischen Legierungsverfahrens | |
DE102011052611A1 (de) | Arbeitskomponente für einen magnetischen Wärmeaustausch und Verfahren zur Erzeugung einer Arbeitskomponente für eine magnetische Kühlung | |
EP2274750A1 (de) | Offenzelliger, poröser formkörper für wärmetauscher | |
EP2467858B1 (de) | Polykristalline magnetokalorische materialien | |
DE112018008152T5 (de) | Seltenerdmagnet, Seltenerd-Sputtermagnet, Seltenerddiffusionsmagnet und Verfahren zur Herstellung | |
DE102018200817A1 (de) | Äußerst hitzebeständiges Seltenerd-Permanentmagnetmaterial, Herstellungsverfahren desselben und Magnet, der dasselbe enthält | |
DE102013009940A1 (de) | Magnetisches Material, seine Verwendung und Verfahren zu dessen Herstellung | |
DE60129506T2 (de) | Herstellungsverfahren für Seltenerd-Dauermagneten | |
DE102014103210B4 (de) | Herstellen von nd-fe-b-magneten unter verwendung von heisspressen mit verringertem dysprosium oder terbium | |
WO2004049359A1 (de) | Verfahren zum herstellen eines anisotropen magnetpulvers und eines gebundenen anisotropen magneten daraus | |
DE2121514B2 (de) | Verfahren zur Herstellung eines intermetallischen Sinterwerkstoffes, insbesondere für Dauermagnete | |
DE69314098T2 (de) | Verfahren zur Herstellung von R-Fe-B-Typ Sintermagneten durch Injektionsformen | |
DE3120168A1 (de) | Magnetische metallegierungsformlinge, verfahren zu deren herstellung und vorrichtung zur durchfuehrung des verfahrens | |
DE2121596A1 (de) | Hartmagnetische legierung | |
DE102006032520B4 (de) | Verfahren zur Herstellung von Magnetkernen, Magnetkern und induktives Bauelement mit einem Magnetkern | |
DE102007047874B4 (de) | Poröser Formkörper aus Metalloxiden und Verfahren zu seiner Herstellung | |
DE69102277T2 (de) | Behandlung von magnetpulvermaterialien und so erhaltene gegenstände. | |
DE102017102163B4 (de) | Magnetokalorischer Wärmeübertrager und Verfahren zu seiner Herstellung | |
DE2429600A1 (de) | In luft stabile, magnetische materialien und verfahren zu deren herstellung | |
EP0243641A1 (de) | Verfahren zur Herstellung eines Dauermagnetwerkstoffes aus pulverförmigen Ausgangskomponenten |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20111122 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: GUTFLEISCH, OLIVER Inventor name: LYUBINA, JULIA |
|
DAX | Request for extension of the european patent (deleted) | ||
17Q | First examination report despatched |
Effective date: 20140617 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20150608 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 762960 Country of ref document: AT Kind code of ref document: T Effective date: 20151215 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 502010010700 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20160225 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151125 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151125 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160325 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160225 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151125 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151125 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151125 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160325 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151125 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151125 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160226 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151125 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151125 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151125 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 502010010700 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151125 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151125 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160430 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151125 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151125 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151125 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20160826 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151125 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20160419 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160419 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20161230 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160430 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160419 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160430 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160502 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160419 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 762960 Country of ref document: AT Kind code of ref document: T Effective date: 20160419 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160419 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151125 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20100419 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151125 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151125 Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151125 Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151125 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151125 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20220519 Year of fee payment: 13 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 502010010700 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20231103 |