EP2422347B1 - Matériau allié magnétique et son procédé de fabrication - Google Patents
Matériau allié magnétique et son procédé de fabrication Download PDFInfo
- Publication number
- EP2422347B1 EP2422347B1 EP10718525.8A EP10718525A EP2422347B1 EP 2422347 B1 EP2422347 B1 EP 2422347B1 EP 10718525 A EP10718525 A EP 10718525A EP 2422347 B1 EP2422347 B1 EP 2422347B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alloy material
- magnetic alloy
- particles
- magnetic
- 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.)
- Not-in-force
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- 239000000956 alloy Substances 0.000 title claims description 76
- 229910001004 magnetic alloy Inorganic materials 0.000 title claims description 61
- 238000000034 method Methods 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000000463 material Substances 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 32
- 239000011159 matrix material Substances 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- 229910052733 gallium Inorganic materials 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910052720 vanadium 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
- 239000011888 foil Substances 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus 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
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 238000005056 compaction Methods 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052758 niobium 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 description 32
- 238000001816 cooling Methods 0.000 description 19
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000013078 crystal Substances 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
- 239000010949 copper Substances 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
- 230000001351 cycling effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910000859 α-Fe Inorganic materials 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 238000005382 thermal cycling Methods 0.000 description 2
- 241001136792 Alle Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017034 MnSn Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000010314 arc-melting process Methods 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
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 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
- 238000001035 drying Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 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
- 238000010348 incorporation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000007689 inspection Methods 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
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000000725 suspension Substances 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 alloy 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 production.
- a magnetic cooling material magnetictocaloric material
- 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 NaZn 13 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 c of the material.
- Magnetic alloy materials of the NaZn 13 type crystal structure are known and could be used as magnetic cooling materials.
- the composition of such materials can be given by the formula R (T 1-a M a ) 13 H d , where R is rare earth elements or a combination of rare earth elements, T is Fe or a combination of Fe and Co and M is Al, Si, Ga or Ge or combinations thereof.
- R rare earth elements or a combination of rare earth elements
- T Fe or a combination of Fe and Co
- M Al, Si, Ga or Ge or combinations thereof.
- 0.05 ⁇ a ⁇ 0.2 and for d, 0 ⁇ d ⁇ 3.0 Such materials have very good magnetocaloric properties at temperatures near the Curie temperature and are considered to be promising candidates for magnetic cooling [ C. Zimm et al., Int. J. Refrigeration 29, 1302 (2006 )].
- such magnetic alloys are produced by means of an arc or high-frequency melting process and then, for example, for about 168 h at about 1050 ° C. under vacuum ( DE 103 38 467 A1 ) heat treated. It is also possible to melt the alloying elements at 1200 to 1800 ° C, then cool the alloy at a cooling rate of 10 2 to 10 6 ° C / s (solidify rapidly) 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, Mn 1 -x Fe x As, Ni 2 MnSn and (Mn, Fe) 2 (P, As) are known, some of which is a particularly large MCE which is caused by a thermally and / or field-induced magnetic phase transition near the Curie temperature T c and / or near a structural phase transition
- MCE magnetic alloys
- 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 in 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 alloy material having improved mechanical properties with comparable magnetic and / or magnetocaloric properties over the prior art materials, and to provide an effective method for producing the magnetic alloy material.
- the magnetic alloy material of the present invention exhibiting a magnetocaloric effect is an alloy material in which particles of the magnetic alloy material are embedded in a matrix material having higher ductility than the magnetic alloy material.
- ⁇ 35 vol .-% of the magnetic alloy material has a crystal structure NaZn 13 type, whereby even more advantageously at least 50 vol .-%, more advantageously from 80 to 90 vol .-%, the magnetic alloy material has a crystal structure NaZn 13 type on.
- the conditions of 2 ⁇ z ⁇ 15 at% and / or 3 ⁇ y ⁇ 16 and / or 0.3 ⁇ x ⁇ 9 are realized to change the Curie temperature of the magnetic alloy material, wherein with varying proportion z and / or y and / or x the Curie temperature changes between 170 K and 400 K.
- 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 of 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.
- particles of the magnetic alloy material are mixed with a matrix material having a 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.
- 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 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 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 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 alloy material 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 NaZn 13 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 affect the Curie temperature T c , which is known to be important for magnetic alloy materials, and which determines the temperature of use by increasing the Curie temperature as the proportion of these elements, and in particular H, increases.
- T c 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 incorporation is also absorbed by the foam-like structure or the matrix material.
- 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.
- hydrogen can be introduced interstitially into the crystal lattice or substitute elements such as Co, Ni, Cu by Fe diffusion processes and thereby increase the Curie temperature T c .
- 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.
- prepared 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 ad decreases slightly.
- a high reproducibility after significantly more work cycles in comparison to a solid material is advantageous.
- a solid material having the composition LaFe 11.6 Si 1.4 is produced by induction melting and subsequent heat treatment at 1050 ° C. for 7 days.
- the resulting material consists of 97 wt .-% of the NaZn 13 -type phase and 3 wt .-% of ⁇ -Fe.
- the solid material with the composition LaFe 11.6 Si 1.4 shows at a magnetic field change of 2 Tesla a maximum entropy change ⁇ S max 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 ad 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 194 K.
- the thermal hysteresis is 3 K and magnetic hysteresis up to 0.7 T.
- ⁇ T ad max decreases to 6.7 K and 6.6 K when cooling from room temperature to 5 K and 4.9 K when heating 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 is produced from the pulverized solid material by hot pressing at a pressing temperature of 600 - 1423 K and a pressing pressure of the order of magnitude of ⁇ 10 2 - 10 3 MPa.
- the resulting material consists of 91% by weight of the NaZn 13 -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 LaFe 11.6 Si 1.4 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 LaFe 11.6 Si 1.4 shows a maximum entropy change ⁇ S max 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 ad also remains unchanged after the thermal and magnetic field alternating stress and amounts to 4.3 K during cooling from room temperature and when heating from 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 LaFe 11.6 Si 1.4 is produced by means of an arc melting process.
- the alloy is then rapidly solidified with the surface speed of the copper wheel of 30 m / s and then heat treated at 1050 ° C for 2 hours.
- the resulting material is in the form of a band having a thickness of 60 microns and consists of 90 wt .-% of the NaZn 13 -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 LaFe 11.6 Si 1.4 alloy are 11 mm diameter x 1 mm height and the density is 85% of the theoretical density of the material.
- the cold-pressed LaFe 11.6 Si 1.4 alloy shows a maximum magnetic entropy change ⁇ S max 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 ad remains unchanged after the thermal and magnetic field alternating stress and is 4.3 K at 193 K on cooling from room temperature and during heating of 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 LaFe 11.6 Si 1.4 alloy is hydrogenated at 400 ° 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 LaFe 11.6 Si 1.4 H 1.64 .
- 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 ad remains unchanged after the thermal and magnetic field cycling and is 3.7 K on cooling Room temperature and when heating from 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 of hydrogen gas and then produced at a temperature of 650 K and a compacting pressure of 500 MPa.
- the adiabatic temperature change ⁇ T ad 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.
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- 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)
Claims (10)
- Matériau d'alliage magnétique, qui comprend des particules ayant une composition selon la formule
RaFe100-a-x-y-zTxMyLz
avecR = La ou une combinaison de La avec Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu et/ou Y,T = au moins un élément choisi dans le groupe Sc, Ti, V, Cr, Mn, Co, Ni, Cu et/ou Zn,M = Al, Si, P, Ga, Ge, In et/ou Sn,L = H, B, C et/ou N,5 ≤ a ≤ 11 et 0 ≤ x ≤ 12 et 2 ≤ y ≤ 20 et 2 ≤ z ≤ 18 (tous en % atomique), qui présentent un effet magnétocalorique, les particules du matériau d'alliage magnétique étant incorporées dans un matériau de matrice de ductilité plus élevée que le matériau d'alliage magnétique. - Matériau d'alliage selon la revendication 1, dans lequel, pour la modification de la température de Curie du matériau d'alliage magnétique, les conditions 2 ≤ z ≤ 15 % atomique et/ou 3 ≤ y ≤ 16 et/ou 0,3 ≤ x ≤ 9 sont réalisées, la température de Curie variant entre 170 K et 400 K lorsque les proportions z et/ou y et/ou x varient.
- Matériau d'alliage selon la revendication 1, dans lequel des particules du matériau d'alliage magnétique d'une taille de particule de 10 nm à 1 mm sont incorporées dans un matériau de matrice.
- Matériau d'alliage selon la revendication 1, dans lequel le matériau de matrice de ductilité plus élevée que le matériau d'alliage magnétique est constitué d'au moins un élément parmi Al, Ag, Au, Bi, C, Co, Cu, Fe, Ga, Ni, Pb, Pd, Pt, Sn, Ti, Zn ou leurs combinaisons et/ou produits de réaction.
- Matériau d'alliage selon la revendication 1, dans lequel, en plus du matériau de matrice, un second matériau d'au moins un élément parmi Al, Ag, Au, Bi, C, Co, Cu, Fe, Ga, Ni, Nb, Pb, Pd, Pt, Sn, Ta, Ti, V, Zn, Zr ou leurs combinaisons et/ou produits de réaction, également avec le matériau de matrice, est présent.
- Matériau d'alliage selon la revendication 1, dans lequel le matériau de matrice présente une ductilité au moins 10 % supérieure au matériau d'alliage magnétique.
- Matériau d'alliage selon la revendication 1, dans lequel les particules du matériau d'alliage magnétique se présentent sous la forme d'une bande, d'un fil, d'une plaque, d'une feuille ou d'un flocon, d'une aiguille ou sous la forme de particules de poudre.
- Procédé de fabrication d'un matériau d'alliage magnétique selon au moins l'une quelconque des revendications 1 à 7, dans lequel des particules du matériau d'alliage magnétique sont mélangées avec un matériau de matrice qui présente une ductilité supérieure au matériau d'alliage magnétique, puis chauffées jusqu'à ce que le matériau de matrice forme la matrice autour des particules du matériau d'alliage magnétique, la température appliquée, qui est déterminée par la température de Curie, étant ajustée par application d'un vide.
- Procédé selon la revendication 8, dans lequel le compactage est réalisé par compression à chaud ou à froid.
- Procédé selon la revendication 8, dans lequel des particules du matériau d'alliage magnétique et du matériau de matrice sont mélangées et transformées en un corps moulé, puis ce corps moulé est porté à une température à laquelle le matériau de matrice est au moins ramolli et recouvre en totalité les particules du matériau d'alliage magnétique.
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 (fr) | 2009-04-24 | 2010-04-19 | Matériau allié magnétique et son procédé de fabrication |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2422347A1 EP2422347A1 (fr) | 2012-02-29 |
EP2422347B1 true EP2422347B1 (fr) | 2015-11-25 |
Family
ID=42224392
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP10718525.8A Not-in-force EP2422347B1 (fr) | 2009-04-24 | 2010-04-19 | Matériau allié magnétique et son procédé de fabrication |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP2422347B1 (fr) |
DE (1) | DE102009002640A1 (fr) |
WO (1) | WO2010121977A1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102015119103A1 (de) * | 2015-11-06 | 2017-05-11 | Technische Universität Darmstadt | Verfahren zum Herstellen eines magnetokalorischen Verbundmaterials und Verbundmaterial mit einem magnetokalorischen Pulver |
CN109313971A (zh) * | 2016-06-10 | 2019-02-05 | 巴斯夫欧洲公司 | 包含锰、铁、硅、磷和碳的磁热材料 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE112009001803B4 (de) | 2009-05-06 | 2023-09-21 | Vacuumschmelze Gmbh & Co. Kg | Verfahren zur Herstellung eines Gegenstandes für magnetischen Wärmeaustausch |
US9245673B2 (en) | 2013-01-24 | 2016-01-26 | Basf Se | Performance improvement of magnetocaloric cascades through optimized material arrangement |
JP6285463B2 (ja) * | 2013-01-24 | 2018-02-28 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | 材料配列の最適化による磁気熱量カスケードの性能改良 |
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 |
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 |
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DE3687680T2 (de) * | 1985-09-30 | 1993-07-08 | Toshiba Kawasaki Kk | Verwendung polykristalliner magnetischer substanzen zur magnetischen abkuehlung. |
EP0870814B1 (fr) * | 1996-10-30 | 2002-06-05 | Kabushiki Kaisha Toshiba | Materiau d'accumulation du froid pour une temperature ultra-basse, machine de refrigeration utilisant ce materiau et materiau de blindage thermique |
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 (fr) | 2002-10-25 | 2013-05-08 | Showa Denko K.K. | Procede de fabrication d'un alliage contenant un element des terres rares |
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 |
JP2010516042A (ja) * | 2007-02-12 | 2010-05-13 | ヴァキュームシュメルツェ ゲーエムベーハー ウント コンパニー カーゲー | 磁気熱交換用構造体及びその製造方法 |
GB2459066B (en) * | 2007-02-12 | 2012-02-15 | Vacuumschmelze Gmbh & Co Kg | Article for magnetic heat exchange and method of manufacturing the same |
WO2009090442A1 (fr) * | 2007-12-27 | 2009-07-23 | Vacuumschmelze Gmbh & Co. Kg | Article composite avec une matière active sur le plan magnétocalorique et son procédé de fabrication |
EP2109119A1 (fr) * | 2008-04-07 | 2009-10-14 | Haute Ecole d'Ingénierie et de Gestion du Canton de Vaud (HEIG-VD) | Matériau magnétocalorique perméable et réfrigérateur magnétique, pompe à chaleur ou générateur de puissance utilisant ce matériau |
-
2009
- 2009-04-24 DE DE200910002640 patent/DE102009002640A1/de not_active Withdrawn
-
2010
- 2010-04-19 EP EP10718525.8A patent/EP2422347B1/fr not_active Not-in-force
- 2010-04-19 WO PCT/EP2010/055086 patent/WO2010121977A1/fr active Application Filing
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102015119103A1 (de) * | 2015-11-06 | 2017-05-11 | Technische Universität Darmstadt | Verfahren zum Herstellen eines magnetokalorischen Verbundmaterials und Verbundmaterial mit einem magnetokalorischen Pulver |
CN109313971A (zh) * | 2016-06-10 | 2019-02-05 | 巴斯夫欧洲公司 | 包含锰、铁、硅、磷和碳的磁热材料 |
Also Published As
Publication number | Publication date |
---|---|
EP2422347A1 (fr) | 2012-02-29 |
DE102009002640A1 (de) | 2011-01-20 |
WO2010121977A1 (fr) | 2010-10-28 |
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