EP2277180B1 - Procédé de fabrication de matériaux à base de métal pour le refroidissement magnétique ou pour pompes à chaleur - Google Patents

Procédé de fabrication de matériaux à base de métal pour le refroidissement magnétique ou pour pompes à chaleur Download PDF

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EP2277180B1
EP2277180B1 EP09738093.5A EP09738093A EP2277180B1 EP 2277180 B1 EP2277180 B1 EP 2277180B1 EP 09738093 A EP09738093 A EP 09738093A EP 2277180 B1 EP2277180 B1 EP 2277180B1
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stage
metal
range
solid
process according
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EP2277180A1 (fr
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Ekkehard BRÜCK
Thanh Trung Nguyen
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Technology Foundation - STW
Universiteit Van Amsterdam
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Technology Foundation - STW
Universiteit Van Amsterdam
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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
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1017—Multiple heating or additional steps
    • B22F3/1028—Controlled cooling
    • 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
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
    • 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
    • B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2200/00—Crystalline structure
    • C22C2200/04—Nanocrystalline
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2202/00—Physical properties
    • C22C2202/02—Magnetic

Definitions

  • the invention relates to processes for the production of metal-based materials for magnetic cooling or heat pumps, such materials and their use.
  • the materials produced according to the invention are used in magnetic cooling, in heat pumps or air conditioning systems.
  • the magnetic cooling techniques are based on the magnetocaloric effect (MCE) and can be an alternative to the known steam-cycle cooling methods.
  • MCE magnetocaloric effect
  • the alignment of randomly oriented magnetic moments with an external magnetic field results in heating of the material. This heat can be dissipated from the MCE material into the ambient atmosphere by heat transfer.
  • the magnetic field is then turned off or removed, the magnetic moments revert to a random arrangement, causing the material to cool to below ambient temperature.
  • This effect can be used for cooling purposes, see also Nature, Vol. 415, 10 January 2002, pages 150 to 152 .
  • a heat transfer medium such as water is used for heat removal from the magnetocaloric material.
  • the preparation of conventional materials is carried out by solid phase reaction of the starting materials or starting alloys for the material in a ball mill, subsequent compression, sintering and annealing under an inert gas atmosphere and subsequent slow cooling to room temperature.
  • Such a method is for example in J. Appl. Phys. 99, 2006, 08Q107 described.
  • the output elements are first induction-melted in an argon gas atmosphere and then sprayed in a molten state via a nozzle onto a rotating copper roll. This is followed by sintering at 1000 ° C and slow cooling to room temperature.
  • US 2006/0076084 relates to an alloy containing rare earth elements.
  • the alloy can be used for magnetic cooling applications.
  • the preparation is carried out according to Example 1 by melt spinning a lanthanum-containing alloy, after which the melt-spun product is sintered for three hours at 1100 ° C. Subsequently, a pulverization is carried out.
  • A. Yan et al., Journal of Applied Physics, Vol. 99, pp. 08 K903-1 to 08908-4 refers to the magnetic entropy change in melt-spun MnFePGe. Melt spinning achieves large magnetocaloric effects, which are attributed to a more homogeneous element distribution due to the very high cooling rate. The spun tapes are tempered for one hour at 1000 ° C and then slowly cooled in the oven.
  • the materials obtained by the known method often show a large thermal hysteresis.
  • thermal hysteresis For example, in Fe 2 P-type compounds substituted with germanium or silicon, large values for thermal hysteresis are observed in a wide range of 10 K or more. Thus, these materials are less suitable for magnetocaloric cooling.
  • the object of the present invention is to provide a method for producing metal-based materials for magnetic cooling, which leads to a reduction of the thermal hysteresis. At the same time, preferably a large magnetocaloric effect (MCE) should be achieved.
  • MCE magnetocaloric effect
  • the thermal hysteresis can be significantly reduced if the metal-based materials are not slowly cooled to ambient temperature after sintering and / or annealing, but are quenched at a high cooling rate. Especially preferred are cooling rates of 300 to 1000 K / s.
  • the quenching can be achieved by any suitable cooling method, for example by quenching the solid with water or aqueous liquids, such as cooled water or ice / water mixtures.
  • the solids can be dropped, for example, in iced water. It is also possible to quench the solids with undercooled gases such as liquid nitrogen. Other quenching methods are known to those skilled in the art.
  • the advantage here is a controlled and rapid cooling.
  • the reduced hysteresis can be attributed to smaller grain sizes for the quenched (quenched) compositions.
  • the rest of the preparation of the metal-based materials is less critical, as long as the quenching of the sintered and / or tempered solid takes place in the last step with the cooling rate according to the invention.
  • the method can be applied to the production of any suitable metal-based materials for magnetic cooling.
  • Typical materials for the magnetic cooling are multimetal materials which often contain at least three metallic elements and optionally also non-metallic elements.
  • the term "metal-based materials" indicates that the majority of these materials are composed of metals or metallic elements.
  • the proportion of the total material is at least 50 wt .-%, preferably at least 75 wt .-%, in particular at least 80 wt .-%. Suitable metal-based materials are explained in more detail below.
  • step (a) of the process according to the invention the reaction of the elements and / or alloys contained in the later metal-based material takes place in a stoichiometry corresponding to the metal-based material in the solid or liquid phase.
  • the reaction in step a) is carried out by co-heating the elements and / or alloys in a closed container or in an extruder, or by solid-phase reaction in a ball mill.
  • a solid phase reaction is carried out, which takes place in particular in a ball mill.
  • powders of the individual elements or powders of alloys of two or more of the individual elements which are present in the later metal-based material are typically mixed in powder form in suitable proportions by weight. If necessary, additional grinding of the mixture can be carried out to obtain a microcrystalline powder mixture.
  • This powder mixture is preferably heated in a ball mill, which leads to a further reduction as well as good mixing and to a solid phase reaction in the powder mixture.
  • the individual elements are mixed in the selected stoichiometry as a powder and then melted.
  • the common heating in a closed container allows the fixation of volatile elements and the control of the stoichiometry. Especially with the use of phosphorus, this would easily evaporate in an open system.
  • the reaction is followed by sintering and / or tempering of the solid, wherein one or more intermediate steps may be provided.
  • the solid obtained in step a) can be pressed before it is sintered and / or tempered.
  • the pressing is known per se and can be carried out with or without pressing aids. In this case, any suitable shape can be used for pressing. By pressing, it is already possible to produce shaped bodies in the desired three-dimensional structure.
  • the pressing may be followed by sintering and / or tempering step c) followed by quenching step d).
  • melt spinning processes are known per se and, for example, in Rare Metals, Vol. 25, October 2006, pages 544 to 549 as well as in WO 2004/068512 described.
  • the composition obtained in step a) is melted and sprayed onto a rotating cold metal roller.
  • This spraying can be achieved by means of positive pressure in front of the spray nozzle or negative pressure behind the spray nozzle.
  • a rotating copper drum or roller is used which, if desired, may be cooled.
  • the copper drum preferably rotates at a surface speed of 10 to 40 m / s, in particular 20 to 30 m / s.
  • the liquid composition is cooled at a rate of preferably 10 2 to 10 7 K / s, more preferably at a rate of at least 10 4 K / s, in particular at a rate of 0.5 to 2 x 10 6 K / s.
  • the melt spinning can be carried out as well as the reaction in step a) under reduced pressure or under an inert gas atmosphere.
  • the Meltspinning a high processing speed is achieved because the subsequent sintering and annealing can be shortened. Especially on an industrial scale so the production of metal-based materials is much more economical. Spray drying also leads to a high processing speed. Particularly preferably, the melt spinning (Melt spinning) is performed.
  • a spray cooling may be carried out, in which a melt of the composition from step a) is sprayed into a spray tower.
  • the spray tower can be additionally cooled, for example.
  • cooling rates in the range of 10 3 to 10 5 K / s, in particular about 10 4 K / s are often achieved.
  • the sintering and / or tempering of the solid takes place in stage c) preferably first at a temperature in the range from 800 to 1400 ° C. for sintering and subsequently at a temperature in the range from 500 to 750 ° C. for tempering.
  • a temperature in the range from 800 to 1400 ° C. for sintering preferably first at a temperature in the range from 800 to 1400 ° C. for sintering and subsequently at a temperature in the range from 500 to 750 ° C. for tempering.
  • sintering may then take place at a temperature in the range of 500 to 800 ° C.
  • shaped bodies / solids sintering is particularly preferably carried out at a temperature in the range from 1000 to 1300 ° C., in particular from 1100 to 1300 ° C.
  • the tempering can then take place at 600 to 700 ° C, for example.
  • the sintering is preferably carried out for a period of 1 to 50 hours, more preferably 2 to 20 hours, especially 5 to 15 hours.
  • the annealing is preferably carried out for a time in the range of 10 to 100 hours, particularly preferably 10 to 60 hours, in particular 30 to 50 hours. Depending on the material, the exact time periods can be adapted to the practical requirements.
  • sintering can often be dispensed with, and tempering can be greatly shortened, for example, for periods of 5 minutes to 5 hours, preferably 10 minutes to 1 hour. Compared to the usual values of 10 hours for sintering and 50 hours for annealing, this results in an extreme time advantage.
  • the sintering / tempering causes the grain boundaries to melt, so that the material continues to densify.
  • stage c By melting and rapid cooling in stage b), the time duration for stage c) can thus be considerably reduced. This also allows for continuous production of the metal-based materials.
  • the method of the invention can be used for any suitable metal-based materials.
  • particularly suitable materials are, for example, in WO 2004/068512 .
  • Rare Metals Vol. 25, 2006, pp. 544-549 .
  • C, D and E are preferably identical or different and selected from at least one of P, Ge, Si, Sn and Ga.
  • the metal-based material of the general formula (I) is preferably selected from at least quaternary compounds which in addition to Mn, Fe, P and optionally Sb also Ge or Si or As or Ge and Si or Ge and As or Si and As or Ge, Si and As included.
  • At least 90% by weight, more preferably at least 95% by weight, of component A are Mn. At least 90% by weight, more preferably at least 95% by weight, of B Fe are preferred. Preferably, at least 90 wt .-%, more preferably at least 95 wt .-% of C P. Preferred are at least 90 wt .-%, more preferably at least 95 wt .-% of D Ge. At least 90% by weight, more preferably at least 95% by weight, of E Si are preferred.
  • the material has the general formula MnFe (P w Ge x Si z ).
  • x is a number in the range of 0.3 to 0.7, w is less than or equal to 1-x and z corresponds to 1-x-w.
  • the material preferably has the crystalline hexagonal Fe 2 P structure.
  • suitable structures are MnFeP 0.45 to 0.7 , Ge 0.55 to 0.30 and MnFeP 0.5 to 0.70 , (Si / Ge) 0.5 to 0.30 .
  • Mn 1 + x Fe 1 -x P 1 -y Ge y where x is in the range of -0.3 to 0.5, y is in the range of 0.1 to 0.6.
  • compounds of the formula Mn 1 + x Fe 1 -x P 1-y Ge yz Si z are suitable with x number in the range of 0.3 to 0.5, y in the range of 0.1 to 0.66, z smaller or equal to y and less than 0.6.
  • La and Fe based compounds of the general formulas (II) and / or (III) and / or (IV) are La (Fe 0.90 Si 0.10 ) 13 , La (Fe 0.89 Si 0.11 ) 13 , La (Fe 0.880 Si 0.120 ) 13 , La (Fe 0.877 Si 0.123 ) 13 , L a F e 11.8 Si 1.2 , La (Fe 0.88 Si 0.12 ) 13 H 0.5 , La (Fe 0.88 Si 0.12 ) 13 H 1.0 , LaFe 11.7 Si 1.3 H 1.1 , LaFe 11.57 Si 1.43 H 1.3 , La (Fe 0.88 Si 0 , 12 ) H 1.5 , LaFe 11.2 Co 0.7 Si 1.1 , LaFe 11.5 Al 1.5 C 0.1 , LaFe 11.5 Al 1.5 C 0.2 , LaFe 11, 5 Al 1.5 C 0.4 , LaFe 11.5 Al 1.5 Co 0.5 , La (Fe 0.94 Co 0.06 ) 11.83 Al
  • Suitable manganese-containing compounds are MnFeGe, MnFe 0.9 Co 0.1 Ge, MnFe 0.8 Co 0.2 Ge, MnFe 0.7 Co 0.3 Ge, MnFe 0.6 Co 0.4 Ge, MnFe 0, 5 Co 0.5 Ge, MnFe 0.4 Co 0.6 Ge, MnFe 0.3 Co 0.7 Ge, MnFe 0.2 Co 0.8 Ge, MnFe 0.15 Co 0.85 Ge, MnFe 0, 1 Co 0.9 Ge, MnCoGe, Mn 5 Ge 2.5 Si 0.5 , Mn 5 Ge 2 Si, Mn 5 Ge 1.5 Si 1.5 , Mn 5 GeSi 2 , Mn 5 Ge 3 , Mn 5 Ge 2.9 Sb 0.1 , Mn 5 Ge 2.5 Si 0.5 , Mn 5 Ge 2 Si, Mn 5 Ge 1.5 Si 1.5 , Mn 5 GeSi 2 , Mn 5 Ge 3 , Mn 5 Ge 2.9 Sb 0.1 , Mn 5 Ge 2.5 Si 0.5 , Mn 5 Ge
  • the disclosure also relates to a metal-based magnetic cooling material obtainable by a method as defined above, as defined above by the composition, except for As-containing materials, having an average crystallite size in the range of 10 to 400 nm, more preferably 20 to 200 nm, in particular 30 to 80 nm.
  • the average crystallite size can be determined by X-ray diffraction. If the crystallite size becomes too small, the maximum magnetocaloric effect is reduced. if the crystallite size is too large, however, the hysteresis of the system increases.
  • the metal-based materials are preferably used in the magnetic cooling as described above.
  • a corresponding refrigerator has in addition to a magnet, preferably permanent magnets, metal-based materials, as described above.
  • the cooling of computer chips and solar power generators is also considered. Further applications are heat pumps and air conditioning systems.
  • the metal-based materials produced by the process according to the invention may have any solid form. They may be present, for example, in the form of flakes, ribbons, wires, powders, as well as in the form of shaped bodies. Shaped bodies such as monoliths or honeycomb bodies can be produced, for example, by a hot extrusion process. For example, cell densities of 400 to 1600 CPI or more may be present. Also obtainable by rolling thin sheets are inventively preferred.
  • Advantageous are non-porous molded body made of molded thin material, eg. As tubes, plates, nets, grids or rods. Shaping by metal injection molding (MIM) is possible according to the invention.
  • MIM metal injection molding
  • Evacuated quartz ampoules containing pressed samples of MnFePGe were kept at 1100 ° C for 10 hours to sinter the powder. This sintering was followed by annealing at 650 ° C for 60 hours to homogenize. However, instead of slowly cooling to room temperature in the oven, the samples were immediately quenched in water at room temperature. Quenching in water caused a degree of oxidation on the sample surfaces. The outer oxidized shell was removed by dilute acid etching. The XRD patterns show that all samples crystallize in a Fe 2 P-type structure.
  • the thermal hysteresis was determined in a magnetic field of 0.5 Tesla.
  • the Curie temperature can be adjusted by varying the Mn / Fe ratio and Ge concentration, as well as the thermal hysteresis value.
  • the change in magnetic entropy calculated from the DC magnetization using the Maxwell relationship for a maximum field change of 0 to 2 Tesla for the first three samples is 14 J / kgK, 20 J / kgK and 12.7 J / kgK, respectively.
  • the MnFePGe compounds show relatively high MCE values in the low field.
  • the thermal hysteresis of these materials is very small.
  • the polycrystalline MnFeP (Ge, Sb) alloys were first prepared in a high energy ball mill and by solid phase reaction techniques as described in U.S. Pat WO 2004/068512 and J. Appl. Phys. 99.08 Q107 (2006 ) are described. The pieces of material were then placed in a quartz tube with a nozzle. The chamber was evacuated to a vacuum of 10 -2 mbar and then filled with argon gas of high purity. The samples were melted by high frequency and sprayed through the nozzle due to a pressure difference to a chamber with a rotating copper drum. The surface speed of the copper wheel could be adjusted and cooling rates of about 10 5 K / s were achieved. Subsequently, the spun ribbons were annealed at 900 ° C for one hour.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Hard Magnetic Materials (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)

Claims (7)

  1. Procédé de fabrication de matériaux à base de métaux pour le refroidissement magnétique ou des pompes à chaleur, comprenant les étapes suivantes :
    a) la mise en réaction d'éléments chimiques et/ou d'alliages en une stoechiométrie qui correspond à celle du matériau à base de métaux, en phase solide et/ou liquide,
    b) éventuellement la transformation du produit de réaction de l'étape a) en un corps solide,
    c) le frittage et/ou le recuit du corps solide de l'étape a) ou b),
    d) la trempe du corps solide fritté et/ou recuit de l'étape c) à une vitesse de refroidissement dans la plage allant de 200 à 1 300 K/s.
  2. Procédé selon la revendication 1, caractérisé en ce que la réaction à l'étape a) a lieu par chauffage conjoint des éléments et/ou des alliages dans un contenant fermé ou dans une extrudeuse, ou par réaction en phase solide dans un broyeur à billes.
  3. Procédé selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que la transformation en un corps solide à l'étape b) a lieu par filage à l'état fondu ou refroidissement par pulvérisation.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'à l'étape c), un frittage est tout d'abord réalisé à une température dans la plage allant de 800 à 1 400 °C, puis un recuit à une température dans la plage allant de 500 à 750 °C.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le matériau à base de métaux est choisi parmi
    (1) les composés de formule générale (I)

            (AyB1-y)2+δCwDxEz     (I)

    avec la signification
    A Mn ou Co,
    B Fe, Cr ou Ni,
    C, D, E au moins deux éléments parmi C, D, E sont différents les uns des autres, ont une concentration non infime et sont choisis parmi P, B, Se, Ge, Ga, Si, Sn, N, As et Sb, au moins un élément parmi C, D et E étant Ge ou Si,
    δ nombre dans la plage allant de -0,1 à 0,1,
    w, x, y, z nombres dans la plage allant de 0 à 1, avec w + x + z = 1 ;
    (2) les composés à base de La et Fe de formules générales (II) et/ou (III) et/ou (IV)

            La(FexSi1-x)13Hy     (II)

    avec
    x nombre de 0,7 à 0,95,
    y nombre de 0 à 3 ;


            La (FexAlyCoz)13 ou La(FexSiyCoz)13     (III)

    avec
    x nombre de 0,7 à 0,95,
    y nombre de 0,05 à 1-x,
    z nombre de 0,005 à 0,5 ;
            LaMnxFe2-xGe     (IV)

    avec
    x nombre de 1,7 à 1,95, et
    (3) les alliages de Heusler de type MnTP avec T un métal de transition et P un métal dopant de type p ayant un compte d'électrons par atome e/a dans la plage allant de 7 à 8,5.
  6. Procédé selon la revendication 5, caractérisé en ce que le matériau à base de métaux est choisi parmi les composés au moins quaternaires de formule générale (I) qui contiennent en plus de Mn, Fe, P et éventuellement Sb, également Ge ou Si ou As ou Ge et As ou Si et As ou Ge, Si et As.
  7. Procédé selon la revendication 1, ayant la séquence de procédé :
    a) la mise en réaction en phase solide d'éléments chimiques et/ou d'alliages en une stoechiométrie qui correspond au matériau à base de métaux, dans un broyeur à billes,
    b) le filage à l'état fondu du matériau obtenu à l'étape a),
    c) le recuit du corps solide de l'étape b) pendant une durée de 10 secondes à 5 heures, à une température dans la plage allant de 430 à 1 200 °C,
    d) la trempe du corps solide recuit de l'étape c) avec une vitesse de refroidissement de 200 à 1 300 K/s.
EP09738093.5A 2008-04-28 2009-04-27 Procédé de fabrication de matériaux à base de métal pour le refroidissement magnétique ou pour pompes à chaleur Active EP2277180B1 (fr)

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EP09738093.5A EP2277180B1 (fr) 2008-04-28 2009-04-27 Procédé de fabrication de matériaux à base de métal pour le refroidissement magnétique ou pour pompes à chaleur

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Application Number Priority Date Filing Date Title
EP08155259 2008-04-28
EP09738093.5A EP2277180B1 (fr) 2008-04-28 2009-04-27 Procédé de fabrication de matériaux à base de métal pour le refroidissement magnétique ou pour pompes à chaleur
PCT/EP2009/055024 WO2009133049A1 (fr) 2008-04-28 2009-04-27 Procédé de fabrication de matériaux à base de métal pour le refroidissement magnétique ou pour pompes à chaleur

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EP2277180B1 true EP2277180B1 (fr) 2017-08-09

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US (1) US20110061775A1 (fr)
EP (1) EP2277180B1 (fr)
JP (1) JP5855457B2 (fr)
KR (1) KR101553091B1 (fr)
CN (1) CN102017025B (fr)
AU (2) AU2009242216C1 (fr)
BR (1) BRPI0911771A2 (fr)
CA (1) CA2721621A1 (fr)
NZ (1) NZ588756A (fr)
TW (1) TWI459409B (fr)
WO (1) WO2009133049A1 (fr)

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US20110041513A1 (en) * 2009-08-18 2011-02-24 Technology Foundation Stw Polycrystalline magnetocaloric materials
TW201145319A (en) 2010-01-11 2011-12-16 Basf Se Magnetocaloric materials
AU2011225713A1 (en) 2010-03-11 2012-08-23 Basf Se Magnetocaloric materials
TWI398609B (zh) * 2010-04-08 2013-06-11 Univ Nat Taipei Technology 室溫下迴轉式磁製冷機裝置
CN101906563B (zh) * 2010-08-31 2013-04-10 沈阳理工大学 一种具有高效室温磁制冷性能的MnAsP化合物的制备方法
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KR101553091B1 (ko) 2015-09-14
AU2009242216B2 (en) 2014-03-20
EP2277180A1 (fr) 2011-01-26
JP5855457B2 (ja) 2016-02-09
NZ588756A (en) 2012-05-25
KR20110036700A (ko) 2011-04-08
AU2009242216A1 (en) 2009-11-05
TWI459409B (zh) 2014-11-01
BRPI0911771A2 (pt) 2015-10-06
TW201009855A (en) 2010-03-01
CN102017025A (zh) 2011-04-13
CN102017025B (zh) 2014-06-25
AU2009242216C1 (en) 2014-09-04
CA2721621A1 (fr) 2009-11-05
US20110061775A1 (en) 2011-03-17
JP2011523676A (ja) 2011-08-18
AU2014203376A1 (en) 2014-07-10
WO2009133049A1 (fr) 2009-11-05

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