EP2277180B1 - Method for producing metal-based materials for magnetic cooling or heat pumps - Google Patents

Method for producing metal-based materials for magnetic cooling or heat pumps Download PDF

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Publication number
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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German (de)
French (fr)
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EP2277180A1 (en
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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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Description

Die Erfindung betrifft Verfahren zur Herstellung von metallbasierten Materialien für die magnetische Kühlung oder Wärmepumpen, derartige Materialien und deren Verwendung. Die erfindungsgemäß hergestellten Materialien werden in der magnetischen Kühlung, in Wärmepumpen oder Klimaanlagen eingesetzt.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.

Derartige Materialien sind prinzipiell bekannt und beispielsweise in WO 2004/068512 beschrieben. Die magnetischen Kühlungstechniken basieren auf dem magnetokalorischen Effekt (MCE) und können eine Alternative zu den bekannten Dampf-Kreislauf-Kühlverfahren darstellen. In einem Material, das einen magnetokalorischen Effekt zeigt, führt die Ausrichtung von zufällig orientierten magnetischen Momenten durch ein externes Magnetfeld zu einem Erwärmen des Materials. Diese Wärme kann vom MCE-Material in die Umgebungsatmosphäre durch einen Wärmetransfer abgeführt werden. Wenn das Magnetfeld daraufhin abgestellt wird oder entfernt wird, gehen die magnetischen Momente wieder in eine Zufallsanordnung über, was zu einem Abkühlen des Materials unter Umgebungstemperatur führt. Dieser Effekt kann zu Kühlzwecken ausgenutzt werden, siehe auch Nature, Vol. 415, 10. Januar 2002, Seiten 150 bis 152 . Typischerweise wird ein Wärmetransfermedium wie Wasser zur Wärmeabfuhr aus dem magnetokalorischen Material eingesetzt.Such materials are known in principle and, for example, in WO 2004/068512 described. The magnetic cooling techniques are based on the magnetocaloric effect (MCE) and can be an alternative to the known steam-cycle cooling methods. In a material exhibiting a 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. When 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 , Typically, a heat transfer medium such as water is used for heat removal from the magnetocaloric material.

Die Herstellung üblicher Materialien erfolgt durch Festphasenumsetzung der Ausgangselemente oder Ausgangslegierungen für das Material in einer Kugelmühle, nachfolgendes Verpressen, Sintern und Tempern unter Inertgasatmosphäre und nachfolgendes langsames Abkühlen auf Raumtemperatur. Ein derartiges Verfahren ist beispielsweise in J. Appl. Phys. 99, 2006, 08Q107 beschrieben.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.

Auch eine Verarbeitung über das Schmelzspinnen ist möglich. Hierdurch ist eine homogenere Elementverteilung möglich, die zu einem verbesserten magnetokalorischen Effekt führt, vergleiche Rare Metals, Vol. 25, Oktober 2006, Seiten 544 bis 549 . In dem dort beschriebenen Verfahren werden zunächst die Ausgangselemente in einer Argongas-atmosphäre induktionsgeschmolzen und sodann in geschmolzenem Zustand über eine Düse auf eine sich drehende Kupferwalze gesprüht. Es folgt ein Sintern bei 1000°C und ein langsames Abkühlen auf Raumtemperatur.Processing by melt spinning is also possible. As a result, a more homogeneous element distribution is possible, which leads to an improved magnetocaloric effect, cf. Rare Metals, Vol. 25, October 2006, pages 544 to 549 , In the process described therein, 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.

D. T. Cam Thanh, Journal of Applied Physics, Bd. 103, Seiten 07 B318-1 bis 07 B318-3 offenbart ein Herstellungsverfahren für MnFeP1-xSix-Verbindungen, wobei zunächst eine Festphasenumsetzung durch hohen Energieeintrag in einer Kugelmühle erfolgt mit nachfolgendem Verpressen und Sintern der Formkörper. Sodann kann entweder langsam abgekühlt werden oder ausgehend von unterschiedlichen Temperaturen gequencht werden. DT Cam Thanh, Journal of Applied Physics, Vol. 103, pages 07 B318-1 to 07 B318-3 discloses a production process for MnFeP 1-x Si x compounds, wherein first a solid phase reaction takes place by high energy input in a ball mill with subsequent pressing and sintering of the moldings. Then it can either be cooled slowly or quenched from different temperatures.

Diese Temperaturen und das Quenchen sind jedoch nicht näher erläutert.However, these temperatures and the quenching are not explained in detail.

US 2006/0076084 betrifft eine Legierung, die Seltenerdelemente enthält. Die Legierung kann für magnetische Kühianwendungen eingesetzt werden. Die Herstellung erfolgt gemäß Beispiel 1 durch Schmelzspinnen einer lanthanhaltigen Legierung, worauf das schmelzgesponnene Produkt für drei Stunden bei 1100°C gesintert wird. Anschließend wird eine Pulverisierung durchgeführt. 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, Bd. 99, Seiten 08 K903-1 bis 08 908-4 betrifft die magnetische Entropieänderung in schmelzgesponnenem MnFePGe. Durch das Schmelzspinnen werden große magnetokalorische Effekte erzielt, die auf eine homogenere Elementverteilung aufgrund der sehr hohen Abkühlrate zurückgeführt werden. Die gesponnenen Bänder werden für eine Stunde bei 1000°C getempert und danach langsam im Ofen abgekühlt. 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.

Die nach dem bekannten Verfahren erhaltenen Materialien zeigen häufig eine große thermische Hysterese. Beispielsweise werden in Verbindungen des Fe2P-Typs, die mit Germanium oder Silicium substituiert sind, große Werte für die thermische Hysterese in einem großen Bereich von 10 K oder mehr beobachtet. Damit sind diese Materialien weniger geeignet zur magnetokalorischen Kühlung.The materials obtained by the known method often show a large 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.

Aufgabe der vorliegenden Erfindung ist die Bereitstellung eines Verfahrens zur Herstellung von metallbasierten Materialien für die magnetische Kühlung, das zu einer Verminderung der thermischen Hysterese führt. Gleichzeitig soll vorzugsweise ein großer magnetokalorischer Effekt (MCE) erreicht werden.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.

Die Aufgabe wird erfindungsgemäß gelöst, gemäß Anspruch 1, durch ein Verfahren zur Herstellung von metallbasierten Materialien für die magnetische Kühlung oder Wärmepumpen, umfassend die folgenden Schritte

  1. a) Umsetzung von chemischen Elementen und/oder Legierungen in einer Stöchiometrie, die dem metallbasierten Material entspricht, in der Fest- und/oder Flüssigphase,
  2. b) gegebenenfalls Überführen des Umsetzungsproduktes aus Stufe a) in einen Festkörper,
  3. c) Sintern und/oder Tempern des Festkörpers aus Stufe a) oder b),
  4. d) Abschrecken des gesinterten und/oder getemperten Festkörpers aus Stufe c) mit einer Abkühlgeschwindigkeit von 200 bis 1300 K/s.
The object is achieved according to the invention, according to claim 1, by a method for the production of metal-based materials for magnetic cooling or heat pumps, comprising the following steps
  1. a) conversion of chemical elements and / or alloys in a stoichiometry corresponding to the metal-based material, in the solid and / or liquid phase,
  2. b) optionally converting the reaction product from stage a) into a solid,
  3. c) sintering and / or annealing the solid from step a) or b),
  4. d) quenching the sintered and / or tempered solid from step c) at a cooling rate of 200 to 1300 K / s.

Es wurde erfindungsgemäß gefunden, dass die thermische Hysterese signifikant vermindert werden kann, wenn die metallbasierten Materialien nach dem Sintern und/oder Tempern nicht langsam auf Umgebungstemperatur abgekühlt werden, sondern mit einer hohen Abkühlgeschwindigkeit abgeschreckt werden. Speziell bevorzugt sind Abkühlgeschwindigkeiten von 300 bis 1000 K/s.It has been found according to the invention that 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.

Das Abschrecken kann dabei durch beliebige geeignete Kühlverfahren erreicht werden, beispielsweise durch Abschrecken des Festkörpers mit Wasser oder wasserhaltigen Flüssigkeiten, beispielsweise gekühltem Wasser oder Eis/Wasser-Mischungen. Die Festkörper können beispielsweise in eisgekühltes Wasser fallengelassen werden. Es ist ferner möglich, die Festkörper mit untergekühlten Gasen wie flüssigem Stickstoff abzuschrecken. Weitere Verfahren zum Abschrecken sind dem Fachmann bekannt. Vorteilhaft ist dabei ein kontrolliertes und schnelles Abkühlen.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.

Ohne an eine Theorie gebunden zu sein, kann die verminderte Hysterese auf kleinere Korngrößen für die abgeschreckten (gequenchten) Zusammensetzungen zurückgeführt werden.Without being bound by theory, the reduced hysteresis can be attributed to smaller grain sizes for the quenched (quenched) compositions.

In den bisher bekannten Verfahren wurde jeweils nach dem Sintern und Tempern langsam abgekühlt, was zur Ausbildung größerer Korngrößen und damit zur Verstärkung der thermischen Hysterese führt.In the previously known methods, the sintering and tempering were slowly cooled in each case, which leads to the formation of larger particle sizes and thus to the enhancement of the thermal hysteresis.

Die übrige Herstellung der metallbasierten Materialien ist weniger kritisch, solange im letzten Schritt das Abschrecken des gesinterten und/oder getemperten Festkörpers mit der erfindungsgemäßen Abkühlgeschwindigkeit erfolgt. Das Verfahren kann dabei auf die Herstellung beliebiger geeigneter metallbasierter Materialien für die magnetische Kühlung angewendet werden. Typische Materialien für die magnetische Kühlung sind Multimetallmassen, die oft mindestens drei metallische Elemente und zusätzlich gegebenenfalls nicht metallische Elemente enthalten. Der Ausdruck "metallbasierte Materialien" gibt an, dass der überwiegende Anteil dieser Materialien aus Metallen bzw. metallischen Elementen aufgebaut ist. Typischerweise beträgt der Anteil am gesamten Material mindestens 50 Gew.-%, bevorzugt mindestens 75 Gew.-%, insbesondere mindestens 80 Gew.-%. Geeignete metallbasierte Materialien sind nachfolgend näher erläutert.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. Typically, 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.

In Schritt (a) des erfindungsgemäßen Verfahrens erfolgt die Umsetzung der Elemente und/oder Legierungen, die im späteren metallbasierten Material enthalten sind, in einer Stöchiometrie, die dem metallbasierten Material entspricht, in der Fest- oder Flüssigphase.In 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.

Vorzugsweise wird die Umsetzung in Stufe a) durch gemeinsames Erhitzen der Elemente und/oder Legierungen in einem geschlossenen Behältnis oder in einem Extruder, oder durch Festphasenumsetzung in einer Kugelmühle erfolgen. Besonders bevorzugt wird eine Festphasenumsetzung durchgeführt, die insbesondere in einer Kugelmühle erfolgt. Eine derartige Umsetzung ist prinzipiell bekannt, vergleiche die einleitend aufgeführten Schriften. Dabei werden typischerweise Pulver der einzelnen Elemente oder Pulver von Legierungen aus zwei oder mehr der einzelnen Elemente, die im späteren metallbasierten Material vorliegen, in geeigneten Gewichtsanteilen pulverförmig vermischt. Falls notwendig, kann zusätzlich ein Mahlen des Gemisches erfolgen, um ein mikrokristallines Pulvergemisch zu erhalten. Dieses Pulvergemisch wird vorzugsweise in einer Kugelmühle aufgeheizt, was zu einer weiteren Verkleinerung wie auch guten Durchmischung und zu einer Festphasenreaktion im Pulvergemisch führt. Alternativ werden die einzelnen Elemente in der gewählten Stöchiometrie als Pulver vermischt und anschließend aufgeschmolzen.Preferably, 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. Particularly preferably, a solid phase reaction is carried out, which takes place in particular in a ball mill. Such an implementation is known in principle, compare the introductory listed writings. In this case, 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. Alternatively, the individual elements are mixed in the selected stoichiometry as a powder and then melted.

Das gemeinsame Erhitzen in einem geschlossenen Behälter erlaubt die Fixierung flüchtiger Elemente und die Kontrolle der Stöchiometrie. Gerade bei Mitverwendung von Phosphor würde dieser in einem offenen System leicht verdampfen.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.

An die Umsetzung schließt sich ein Sintern und/oder Tempern des Festkörpers an, wobei ein oder mehrere Zwischenschritte vorgesehen sein können. Beispielsweise kann der in Stufe a) erhaltene Feststoff verpresst werden, bevor er gesintert und/oder getempert wird. Hierdurch wird die Dichte des Materials erhöht, so dass bei der späteren Anwendung eine hohe Dichte des magnetokalorischen Materials vorliegt. Dies ist insbesondere deshalb vorteilhaft, da das Volumen, in dem das magnetische Feld herrscht, vermindert werden kann, was mit erheblichen Kosteneinsparungen verbunden sein kann. Das Verpressen ist an sich bekannt und kann mit oder ohne Presshilfsmittel durchgeführt werden. Dabei kann jede beliebige geeignete Form zum Pressen verwendet werden. Durch das Verpressen ist es bereits möglich, Formkörper in der gewünschten dreidimensionalen Struktur zu erzeugen. An das Verpressen kann sich das Sintern und/oder Tempern der Stufe c) gefolgt vom Abschrecken der Stufe d) anschließen.The reaction is followed by sintering and / or tempering of the solid, wherein one or more intermediate steps may be provided. For example, the solid obtained in step a) can be pressed before it is sintered and / or tempered. As a result, the density of the material is increased, so that there is a high density of the magnetocaloric material in the subsequent application. This is particularly advantageous because the volume in which the magnetic field prevails can be reduced, which can be associated with significant cost savings. 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).

Alternativ ist es möglich, den aus der Kugelmühle erhaltenen Feststoff einem Schmelzspinnverfahren zuzuführen. Schmelzspinnverfahren sind an sich bekannt und beispielsweise in Rare Metals, Vol. 25, Oktober 2006, Seiten 544 bis 549 wie auch in WO 2004/068512 beschrieben.Alternatively, it is possible to feed the solid obtained from the ball mill to a melt spinning process. 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.

Dabei wird die in Stufe a) erhaltene Zusammensetzung geschmolzen und auf eine sich drehende kalte Metallwalze gesprüht. Dieses Sprühen kann mittels Überdruck vor der Sprühdüse oder Unterdruck hinter der Sprühdüse erreicht werden. Typischerweise wird eine sich drehende Kupfertrommel oder -walze verwendet, die zudem gegebenenfalls gekühlt werden kann. Die Kupfertrommel dreht sich bevorzugt mit einer Oberflächengeschwindigkeit von 10 bis 40 m/s, insbesondere 20 bis 30 m/s. Auf der Kupfertrommel wird die flüssige Zusammensetzung mit einer Geschwindigkeit von vorzugsweise 102 bis 107 K/s abgekühlt, besonders bevorzugt mit einer Geschwindigkeit von mindestens 104 K/s, insbesondere mit einer Geschwindigkeit von 0,5 bis 2 x 106 K/s.In this case, 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. Typically, 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. On the copper drum, 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.

Das Schmelzspinnen kann wie auch die Umsetzung in Stufe a) unter vermindertem Druck oder unter Inertgasatmosphäre durchgeführt werden.The melt spinning can be carried out as well as the reaction in step a) under reduced pressure or under an inert gas atmosphere.

Durch das Meltspinning wird eine hohe Verarbeitungsgeschwindigkeit erreicht, da das nachfolgende Sintern und Tempern verkürzt werden kann. Gerade im technischen Maßstab wird so die Herstellung der metallbasierten Materialien wesentlich wirtschaftlicher. Auch die Sprühtrocknung führt zu einer hohen Verarbeitungsgeschwindigkeit. Besonders bevorzugt wird das Schmelzespinnen (Melt spinning) durchgeführt.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.

Alternativ kann in Stufe b) ein Sprühkühlen durchgeführt werden, bei dem eine Schmelze der Zusammensetzung aus Stufe a) in einen Sprühturm gesprüht wird. Der Sprühturm kann dabei beispielsweise zusätzlich gekühlt werden. In Sprühtürmen werden häufig Abkühlgeschwindigkeiten im Bereich von 103 bis 105 K/s, insbesondere etwa 104 K/s erreicht.Alternatively, in step b), 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. In spray towers cooling rates in the range of 10 3 to 10 5 K / s, in particular about 10 4 K / s are often achieved.

Das Sintern und/oder Tempern des Festkörpers erfolgt in Stufe c) vorzugsweise zunächst bei einer Temperatur im Bereich von 800 bis 1400 °C zum Sintern und nachfolgend bei einer Temperatur im Bereich von 500 bis 750 °C zum Tempern. Diese Werte gelten insbesondere für Formkörper, während für Pulver niedrigere Sinter- und Tempertemperaturen angewendet werden können. Beispielsweise kann dann das Sintern bei einer Temperatur im Bereich von 500 bis 800 °C erfolgen. Für Formkörper/Festkörper erfolgt das Sintern besonders bevorzugt bei einer Temperatur im Bereich von 1000 bis 1300 °C, insbesondere von 1100 bis 1300 °C. Das Tempern kann dann beispielsweise bei 600 bis 700 °C erfolgen.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. These values apply in particular to shaped bodies, while for powders lower sintering and tempering temperatures can be used. For example, sintering may then take place at a temperature in the range of 500 to 800 ° C. For 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.

Das Sintern wird vorzugsweise für einen Zeitraum von 1 bis 50 Stunden, besonders bevorzugt 2 bis 20 Stunden, insbesondere 5 bis 15 Stunden durchgeführt. Das Tempern wird vorzugsweise für eine Zeit im Bereich von 10 bis 100 Stunden, besonders bevorzugt 10 bis 60 Stunden, insbesondere 30 bis 50 Stunden durchgeführt. Die exakten Zeiträume können dabei je nach Material den praktischen Anforderungen angepasst werden.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.

Bei Einsatz des Schmelzspinnverfahrens kann auf ein Sintern häufig verzichtet werden, und das Tempern kann stark verkürzt werden, beispielsweise auf Zeiträume von 5 Minuten bis 5 Stunden, bevorzugt 10 Minuten bis 1 Stunde. Im Vergleich zu den sonst üblichen Werten von 10 Stunden für das Sintern und 50 Stunden für das Tempern resultiert ein extremer Zeitvorteil.When using the melt spinning method, 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.

Durch das Sintern/Tempern kommt es zu einem Anschmelzen der Korngrenzen, so dass sich das Material weiter verdichtet.The sintering / tempering causes the grain boundaries to melt, so that the material continues to densify.

Durch das Schmelzen und schnelle Abkühlen in Stufe b) kann damit die Zeitdauer für Stufe c) erheblich vermindert werden. Dies ermöglicht auch eine kontinuierliche Herstellung der metallbasierten Materialien.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.

Erfindungsgemäß besonders bevorzugt ist die Verfahrenssequenz

  1. a) Festphasenumsetzung von chemischen Elementen und/oder Legierungen in einer Stöchiometrie, die dem metallbasierten Material entspricht, in einer Kugelmühle,
  2. b) Schmelzspinnen des in Stufe a) erhaltenen Materials,
  3. c) Tempern des Festkörpers aus Stufe b) für einen Zeitraum von 10 Sekunden oder 1 Minute bis 5 Stunden, bevorzugt 30 Minuten bis 2 Stunden bei einer Temperatur im Bereich von 430 bis 1200, bevorzugt 800 bis 1000 °C
  4. d) Abschrecken des getemperten Festkörpers aus Stufe c) mit einer Abkühlgeschwindigkeit von 200 bis 1300 K/s.
Particularly preferred according to the invention is the process sequence
  1. a) solid phase reaction of chemical elements and / or alloys in a stoichiometry, which corresponds to the metal-based material, in a ball mill,
  2. b) melt spinning the material obtained in step a),
  3. c) annealing the solid from step b) for a period of 10 seconds or 1 minute to 5 hours, preferably 30 minutes to 2 hours at a temperature in the range of 430 to 1200, preferably 800 to 1000 ° C.
  4. d) quenching the tempered solid from step c) with a cooling rate of 200 to 1300 K / s.

Das erfindungsgemäße Verfahren kann für beliebige geeignete metallbasierte Materialien verwendet werden.The method of the invention can be used for any suitable metal-based materials.

Besonders bevorzugt ist das metallbasierte Material ausgewählt aus

  1. (1) Verbindungen der allgemeinen Formel (I)

            (AyB1-y)2+δCwDxEz     (I)

    mit der Bedeutung
    A
    Mn oder Co,
    B
    Fe, Cr oder Ni,
    C, D, E
    mindestens zwei von C, D, E sind voneinander verschieden, haben eine nicht-verschwindende Konzentration und sind ausgewählt aus P, B, Se, Ge, Ga, Si, Sn, N, As und Sb, wobei mindestens eines von C, D und E Ge oder Si ist,
    δ
    Zahl im Bereich von - 0,1 bis 0,1
    w, x, y, z
    Zahlen im Bereich von 0 bis 1, wobei w + x + z = 1 ist;
  2. (2) auf La und Fe basierenden Verbindungen der allgemeinen Formeln (II) und/oder (III) und/oder (IV)

            La(FexAl1-x)13Hy oder La(FexSi1-x)13Hy     (II)

    mit
    x
    Zahl von 0,7 bis 0,95
    y
    Zahl von 0 bis 3, vorzugsweise 0 bis 2;


            La(FexAlyCoz)13 oder La(FexSiyCoz)13     (III)

    mit
    x
    Zahl von 0,7 bis 0,95
    y
    Zahl von 0,05 bis 1 - x
    z
    Zahl von 0,005 bis 0,5;


            LaMnxFe2-xGe     (IV)

    mit
    x
    Zahl von 1,7 bis 1,95 und
  3. (3) Heusler-Legierungen des Typs MnTP mit T Übergangsmetall und P einem p-dotierenden Metall mit einem electron count pro Atom e/a im Bereich von 7 bis 8,5.
Particularly preferably, the metal-based material is selected from
  1. (1) Compounds of the general formula (I)

    (A y B 1-y ) 2 + δ C w D x E z (I)

    with the meaning
    A
    Mn or Co,
    B
    Fe, Cr or Ni,
    C, D, E
    at least two of C, D, E are different from each other, have a non-vanishing concentration, and are selected from P, B, Se, Ge, Ga, Si, Sn, N, As, and Sb, with at least one of C, D, and E is Ge or Si,
    δ
    Number in the range of - 0.1 to 0.1
    w, x, y, z
    Numbers ranging from 0 to 1, where w + x + z = 1;
  2. (2) La and Fe based compounds of the general formulas (II) and / or (III) and / or (IV)

    La (Fe x Al 1-x ) 13 H y or La (Fe x Si 1-x ) 13 H y (II)

    With
    x
    Number from 0.7 to 0.95
    y
    Number from 0 to 3, preferably 0 to 2;


    La (Fe x Al y Co z ) 13 or La (Fe x Si y Co z ) 13 (III)

    With
    x
    Number from 0.7 to 0.95
    y
    Number from 0.05 to 1 - x
    z
    Number from 0.005 to 0.5;


    LaMn x Fe 2-x Ge (IV)

    With
    x
    Number from 1.7 to 1.95 and
  3. (3) Heusler alloys of the type MnTP with T transition metal and P a p-doping metal with an electron count per atom e / a in the range of 7 to 8.5.

Erfindungsgemäß besonders geeignete Materialien sind beispielsweise in WO 2004/068512 , Rare Metals, Vol. 25, 2006, Seiten 544 bis 549 , J. Appl. Phys. 99,08Q107 (2006 ), Nature, Vol. 415, 10. Januar 2002, Seiten 150 bis 152 und Physica B 327 (2003), Seiten 431 bis 437 beschrieben.According to the invention particularly suitable materials are, for example, in WO 2004/068512 . Rare Metals, Vol. 25, 2006, pp. 544-549 . J. Appl. Phys. 99.08 Q107 (2006 ) Nature, Vol. 415, 10 January 2002, pages 150 to 152 and Physica B 327 (2003), pages 431 to 437 described.

In den vorstehend genannten Verbindungen der allgemeinen Formel (I) sind bevorzugt C, D und E identisch oder unterschiedlich und ausgewählt aus mindestens einem von P, Ge, Si, Sn und Ga.In the aforementioned compounds of the general formula (I), C, D and E are preferably identical or different and selected from at least one of P, Ge, Si, Sn and Ga.

Das metallbasierte Material der allgemeinen Formel (I) ist vorzugsweise ausgewählt aus mindestens quarternären Verbindungen, die neben Mn, Fe, P und gegebenenfalls Sb zudem Ge oder Si oder As oder Ge und Si oder Ge und As oder Si und As oder Ge, Si und As enthalten.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.

Bevorzugt sind mindestens 90 Gew.-%, besonders bevorzugt mindestens 95 Gew.-% der Komponente A Mn. Bevorzugt sind mindestens 90 Gew.-%, besonders bevorzugt mindestens 95 Gew.-% von B Fe. Bevorzugt sind mindestens 90 Gew.-%, besonders bevorzugt mindestens 95 Gew.-% von C P. Bevorzugt sind mindestens 90 Gew.-%, besonders bevorzugt mindestens 95 Gew.-% von D Ge. Bevorzugt sind mindestens 90 Gew.-%, besonders bevorzugt mindestens 95 Gew.-% von E Si.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.

Vorzugsweise hat das Material die allgemeine Formel MnFe(PwGexSiz).Preferably, the material has the general formula MnFe (P w Ge x Si z ).

Bevorzugt ist x eine Zahl im Bereich von 0,3 bis 0,7, w ist kleiner oder gleich 1-x und z entspricht 1-x-w.Preferably, 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.

Das Material hat vorzugsweise die kristalline hexagonale Fe2P-Struktur. Beispiele geeigneter Strukturen sind MnFeP0,45 bis 0,7, Ge0,55 bis 0,30 und MnFeP0,5 bis 0,70, (Si/Ge)0,5 bis 0,30.The material preferably has the crystalline hexagonal Fe 2 P structure. Examples of 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 .

Geeignete Verbindungen sind ferner Mn1+xFe1-xP1-yGey mit x im Bereich von -0,3 bis 0,5, y im Bereich von 0,1 bis 0,6. Ebenfalls geeignet sind Verbindungen der allgemeinen Formel Mn1+xFe1-xP1-yGey-zSbz mit x im Bereich von -0,3 bis 0,5, y im Bereich von 0,1 bis 0,6 und z kleiner als y und kleiner als 0,2. Ferner sind Verbindungen der Formel Mn1+xFe1-xP1-yGey-zSiz geeignet mit x Zahl im Bereich von 0,3 bis 0,5, y im Bereich von 0,1 bis 0,66, z kleiner oder gleich y und kleiner als 0,6.Other suitable compounds are 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. Also suitable are compounds of the general formula Mn 1 + x Fe 1 -x P 1-y Ge yz Sb z with x in the range of -0.3 to 0.5, y in the range of 0.1 to 0.6 and z less than y and less than 0.2. Furthermore, 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.

Bevorzugte auf La und Fe basierende Verbindungen der allgemeinen Formeln (II) und/oder (III) und/oder (IV) sind La(Fe0,90Si0,10)13, La(Fe0,89Si0,11)13, La(Fe0,880Si0,120)13, La(Fe0,877Si0,123)13, L a F e11,8Si1,2, La(Fe0,88Si0,12)13H0,5, La(Fe0,88Si0,12)13H1,0, LaFe11,7Si1,3H1,1, LaFe11,57Si1,43H1,3, La(Fe0,88Si0,12)H1,5, LaFe11,2Co0,7Si1,1, LaFe11,5Al1,5C0,1, LaFe11,5Al1,5C0,2, LaFe11,5Al1,5C0,4, LaFe11,5Al1,5Co0,5, La(Fe0,94Co0,06)11,83Al1,17, La(Fe0,92Co0,08)11,83Al1,17.Preferred 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 1.17 , La (Fe 0.92 Co 0 , 08 ) 11.83 Al 1.17 .

Geeignete Mangan enthaltende Verbindungen sind MnFeGe, MnFe0,9Co0,1Ge, MnFe0,8Co0,2Ge, MnFe0,7Co0,3Ge, MnFe0,6Co0,4Ge, MnFe0,5Co0,5Ge, MnFe0,4Co0,6Ge, MnFe0,3Co0,7Ge, MnFe0,2Co0,8Ge, MnFe0,15Co0,85Ge, MnFe0,1Co0,9Ge, MnCoGe, Mn5Ge2,5Si0,5, Mn5Ge2Si, Mn5Ge1,5Si1,5, Mn5GeSi2, Mn5Ge3, Mn5Ge2,9Sb0,1, Mn5Ge2,5Si0,5, Mn5Ge2Si, Mn5Ge1,5Si1,5, Mn5GeSi2, Mn5Ge3, Mn5Ge2,9Sb0,1, Mn5Ge2,8Sb0,2, Mn5Ge2,7Sb0,3, LaMn1,9Fe0,1Ge, LaMn1,85Fe0,15Ge, LaMn1,8Fe0,2Ge, (Fe0,9Mn0,1)3C, (Fe0,8Mn0,2)C, (Fe0,7Mn0,3)3C, Mn3GaC, MnAs, (Mn, Fe)As, Mn1+δAs0,8Sb0,2, MnAs0,75Sb0,25, Mn1,1As0,75Sb0,25, Mn1,5As0,75Sb0,25.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 2.8 Sb 0.2 , Mn 5 Ge 2.7 Sb 0.3 , LaMn 1.9 Fe 0.1 Ge, LaMn 1.85 Fe 0.15 Ge, LaMn 1.8 Fe 0.2 Ge , (Fe 0.9 Mn 0.1 ) 3 C, (Fe 0.8 Mn 0.2 ) C, (Fe 0.7 Mn 0.3 ) 3 C, Mn 3 GaC, MnAs, (Mn, Fe) As, Mn 1 + δ As 0.8 Sb 0.2 , MnAs 0.75 Sb 0.25 , Mn 1.1 As 0.75 Sb 0.25 , Mn 1.5 As 0.75 Sb 0.25 .

Erfindungsgemäß geeignete Heusler-Legierungen sind beispielsweise Fe2MnSi0,5Ge0,5, Ni52,9Mn22,4Ga24,7, Ni50,9Mn24,7Ga24,4, Ni55,2Mn18,6Ga26,2, Ni51,6Mn24,7Ga23,8, Ni52,7Mn23,9Ga23,4, CoMnSb, CoNb0,2Mn0,8Sb, CoNb0,4Mn0,6SB, CoNb0,6Mn0,4Sb, Ni50Mn35Sn15, Ni50Mn37Sn13, MnFeP0,45As0,55, MnFeP0,47AS0,53, Mn1,1Fe0,9P0,47As0,53, MnFeP0,89-χSiχGe0,11, χ = 0,22, χ = 0,26, χ = 0,30, χ = 0,33.Heusler alloys suitable according to the invention are, for example, Fe 2 MnSi 0.5 Ge 0.5 , Ni 52.9 Mn 22.4 Ga 24.7 , Ni 50.9 Mn 24.7 Ga 24.4 , Ni 55.2 Mn 18 , 6 Ga 26.2 , Ni 51.6 Mn 24.7 Ga 23.8 , Ni 52.7 Mn 23.9 Ga 23.4 , CoMnSb, CoNb 0.2 Mn 0.8 Sb, CoNb 0.4 Mn 0.6 SB, CoNb 0.6 Mn 0.4 Sb, Ni 50 Mn 35 Sn 15 , Ni 50 Mn 37 Sn 13 , MnFeP 0.45 As 0.55 , MnFeP 0.47 AS 0.53 , Mn 1, 1 Fe 0.9 P 0.47 As 0.53 , MnFeP 0.89-χ Si χ Ge 0.11 , χ = 0.22, χ = 0.26, χ = 0.30, χ = 0.33 ,

Die Offenbarung betrifft auch ein metallbasiertes Material für die magnetische Kühlung, das erhältlich ist nach einem wie vorstehend beschriebenen Verfahren, wie es vorstehend anhand der Zusammensetzung definiert ist, ausgenommen As enthaltende Materialien, mit einer durchschnittlichen Kristallitgröße im Bereich von 10 bis 400 nm, besonders bevorzugt 20 bis 200 nm, insbesondere 30 bis 80 nm. Die durchschnittliche Kristallitgröße kann dabei durch Röntgendiffraktion ermittelt werden. Wird die Kristallitgröße zu klein, so vermindert sich der maximale magnetokalorische Effekt. ist die Kristallitgröße hingegen zu groß, steigt die Hysterese des Systems an.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.

Die metallbasierten Materialien werden bevorzugt in der magnetischen Kühlung eingesetzt, wie sie vorstehend beschrieben wurde. Ein entsprechender Kühlschrank weist dabei neben einem Magneten, vorzugsweise Permanentmagneten, metallbasierte Materialien auf, wie sie vorstehend beschrieben sind. Auch die Kühlung von Computerchips und solaren Stromerzeugern kommt in Betracht. Weitere Anwendungsgebiete sind Wärmepumpen und Klimaanlagen.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.

Die nach dem erfindungsgemäßen Verfahren hergestellten metallbasierten Materialien können jede beliebige Festkörperform aufweisen. Sie können beispielsweise in Form von Flocken, Bändern, Drähten, Puder, Pulver wie auch in Form von Formkörpern vorliegen. Formkörper wie Monolithen oder Wabenkörper können beispielsweise durch ein Heißextrusionsverfahren hergestellt werden. Es können beispielsweise Zelldichten von 400 bis 1600 CPI oder mehr vorliegen. Auch durch Walzverfahren erhältliche dünne Bleche sind erfindungsgemäß bevorzugt. Vorteilhaft sind nicht-poröse Formkörper aus geformtem dünnem Material, z. B. Röhren, Platten, Netze, Gitter oder Stäbe. Auch eine Formgebung durch Metallspritzgussverfahren (MIM) ist erfindungsgemäß möglich.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.

Die Erfindung wird durch die nachstehenden Beispiele näher erläutert.The invention is further illustrated by the following examples.

BeispieleExamples Beispiel 1example 1

Evakuierte Quarzampullen, die gepresste Proben von MnFePGe enthielten, wurden für 10 Stunden bei 1100 °C gehalten, um das Pulver zu sintern. Auf dieses Sintern folgte ein Tempern bei 650 °C für 60 Stunden, um eine Homogenisierung herbeizuführen. Anstelle eines langsamen Abkühlens im Ofen auf Raumtemperatur wurden die Proben jedoch sofort in Wasser bei Raumtemperatur gequencht. Das Quenchen in Wasser verursachte einen gewissen Grad von Oxidation an den Probenoberflächen. Die äußere oxidierte Schale wurde durch Ätzen mit verdünnter Säure entfernt. Die XRD-Muster zeigen, dass alle Proben in einer Struktur des Fe2P-Typs kristallisieren.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.

Folgende Zusammensetzungen wurden dabei erhalten:

  • Mn1,1Fe0,9P0,81Ge0,19; Mn1.1Fe0.9P0.78Ge0.22, Mn1,1Fe0,9P0,75Ge0,25 und Mn1,2Fe0,8P0,81Ge0,19. Die beobachteten Werte für die thermische Hysterese sind für diese Proben in der angegebenen Reihenfolge 7 K, 5 K, 2 K und 3 K. Gegenüber einer langsam abgekühlten Probe war die eine thermische Hysterese von mehr als 10 K aufweist, konnte die thermische Hysterese stark vermindert werden.
The following compositions were obtained:
  • Mn 1.1 Fe 0.9 P 0.81 Ge 0.19 ; Mn 1.1 Fe 0.9 P 0.78 Ge 0.22 , Mn 1.1 Fe 0.9 P 0.75 Ge 0.25 and Mn 1.2 Fe 0.8 P 0.81 Ge 0.19 . The observed values for the thermal hysteresis are 7 K, 5 K, 2 K and 3 K for these samples in the order given. Compared to a slowly cooled sample which had a thermal hysteresis of more than 10 K, the thermal hysteresis could be greatly reduced become.

Die thermische Hysterese wurde dabei in einem Magnetfeld von 0,5 Tesla bestimmt.The thermal hysteresis was determined in a magnetic field of 0.5 Tesla.

Die Curie-Temperatur kann durch Variation des Mn/Fe-Verhältnisses und der Ge-Konzentration eingestellt werden, ebenso der Wert für die thermische Hysterese.The Curie temperature can be adjusted by varying the Mn / Fe ratio and Ge concentration, as well as the thermal hysteresis value.

Die Änderung der magnetischen Entropie, berechnet aus der Gleichstrommagnetisierung unter Verwendung der Maxwell-Beziehung beträgt für eine maximale Feldänderung von 0 bis 2 Tesla für die ersten drei Proben 14 J/kgK, 20 J/kgK bzw. 12,7 J/kgK.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.

Die Curie-Temperatur und die thermische Hysterese nehmen mit zunehmendem Mn/Fe-Verhältnis ab. Im Ergebnis zeigen die MnFePGe-Verbindungen relativ große MCE-Werte in niedrigem Feld. Die thermische Hysterese dieser Materialien ist sehr klein.The Curie temperature and the thermal hysteresis decrease with increasing Mn / Fe ratio. As a result, the MnFePGe compounds show relatively high MCE values in the low field. The thermal hysteresis of these materials is very small.

Beispiel 2Example 2 Schmelzspinnen von MnFeP(GeSb)Melt spinning of MnFeP (GeSb)

Die polykristallinen MnFeP(Ge,Sb)-Legierungen wurden zunächst in einer Kugelmühle mit hohem Energie-Eintrag und durch Festphasenreaktionsverfahren hergestellt, wie sie in WO 2004/068512 und J. Appl. Phys. 99,08 Q107 (2006 ) beschrieben sind. Die Materialstücke wurden sodann in ein Quarzrohr mit einer Düse gegeben. Die Kammer wurde auf ein Vakuum von 10-2 mbar evakuiert und anschließend mit Argongas hoher Reinheit gefüllt. Die Proben wurden durch Hochfrequenz geschmolzen und durch die Düse versprüht aufgrund einer Druckdifferenz zu einer Kammer mit einer rotierenden Kupfertrommel. Die Oberflächengeschwindigkeit des Kupferrades konnte eingestellt werden, und Abkühlgeschwindigkeiten von etwa 105 K/s wurden erreicht. Anschließend wurden die gesponnenen Bänder bei 900 °C für eine Stunde getempert.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.

Aus der Röntgendiffraktometrie geht hervor, dass alle Proben im hexagonalen Fe2P-Strukturmuster kristallisieren. Im Unterschied zu nicht nach dem Schmelzspinnverfahren hergestellten Proben, wurde keine kleinere Verunreinigungsphase von MnO beobachtet.X-ray diffractometry shows that all samples crystallize in the hexagonal Fe 2 P structural pattern. Unlike samples prepared by the melt spinning method, no minor impurity phase of MnO was observed.

Die erhaltenen Werte für die Curie-Temperatur, die Hysterese und die Entropie wurden für unterschiedliche Umfangsgeschwindigkeiten beim Schmelzspinnen bestimmt. Die Ergebnisse sind in den nachstehenden Tabellen 1 und 2 aufgeführt. Jeweils wurden geringe Hysterese-Temperaturen bestimmt. Tabelle 1: Bänder V (m/s) Tc (K) ΔThys (K) -ΔS(J/kgK) Mn1,2Fe0,8P0,73Ge0,25Sb0,02 30 269 4 12,1 Mn1,2Fe0,8P0,70Ge0,20Sb0,10 30 304 4,5 19,0 45 314 3 11,0 MnFeP0,70Ge0,20Sb0,10 20 306 8 17,2 30 340 3 9,5 MnFeP0,75Ge0,25 20 316 9 13,5 40 302 8 - Mn1,1Fe0,9P0,78Ge0,22 20 302 5 - 40 299 7 - Mn1,1Fe0,9P0,75Ge0,25 30 283 9 11,2 Mn1,2Fe0,8P0,75Ge0,25 30 240 8 14,2 Mn1,1Fe0,9P0,73Ge0,27 30 262 5 10,1 Bulk Tc (K) ΔThys (K) -ΔS(J/kgK) MnFeP0,75Ge0,25 327 3 11,0 Mn1,1Fe0,9P0,81Ge0,19 260 7 14,0 Mn1,1Fe0,9P0,78Ge0,22 296 5 20,0 Mn1,1Fe0,9P0,75Ge0,25 330 2 13,0 Mn1,2Fe0,8P0,81Ge0,19 220 3 7,7 Mn1,2Fe0,8P0,75Ge0,25 305 3 - Mn1,2Fe0,8P0,73Ge0,27 313 5 - Mn1,3Fe0,7P0,78Ge0,22 203 3 5,1 Mn1,3Fe0,7P0,75Ge0,25 264 1 - Tabelle 2 Bulk Tc (K) ΔThys (K) -ΔS(J/kgK) MnFeP0,75Ge0,25 327 3 11,0 Mn1,16Fe0,84P0,75Ge0,25 330 5 22,5 Mn1,18Fe0,82P0,75Ge0,25 310 3 16,1 Mn1,20Fe0,80P0,75Ge0,25 302 1 12,0 Mn1,22Fe0,78P0,75Ge0,25 276 4 11,7 Mn1,26Fe0,74P0,75Ge0,25 270 1 8,5 Mn1,1Fe0,9P0,81Ge0,19 260 6 13,8 Mn1,1Fe0,9P0,78Ge0,22 296 4 20,0 Mn1,1Fe0,9P0,77Ge0,23 312 2 14,6 Mn1,1Fe0,9P0,75Ge0,25 329 2 13,0 Bänder Mn1,20Fe0,80P0,75Ge0,25 288 1 20,3 Mn1,22Fe0,78P0,75Ge0,25 274 2 15,3 Mn1,24Fe0,76P0,75Ge0,25 254 2 16,4 Mn1,26Fe0,74P0,75Ge0,25 250 4 14,4 Mn1,30Fe0,70P0,75Ge0,25 230 0 9,8 The values obtained for the Curie temperature, hysteresis and entropy were determined for different melt spinning peripheral speeds. The results are shown in Tables 1 and 2 below. In each case low hysteresis temperatures were determined. Table 1: bands V (m / s) T c (K) ΔT hys (K) -ΔS (J / kgK) Mn 1.2 Fe 0.8 P 0.73 Ge 0.25 Sb 0.02 30 269 4 12.1 Mn 1.2 Fe 0.8 P 0.70 Ge 0.20 Sb 0.10 30 304 4.5 19.0 45 314 3 11.0 MnFeP 0.70 Ge 0.20 Sb 0.10 20 306 8th 17.2 30 340 3 9.5 MnFeP 0.75 Ge 0.25 20 316 9 13.5 40 302 8th - Mn 1.1 Fe 0.9 P 0.78 Ge 0.22 20 302 5 - 40 299 7 - Mn 1.1 Fe 0.9 P 0.75 Ge 0.25 30 283 9 11.2 Mn 1.2 Fe 0.8 P 0.75 Ge 0.25 30 240 8th 14.2 Mn 1.1 Fe 0.9 P 0.73 Ge 0.27 30 262 5 10.1 Bulk T c (K) ΔT hys (K) -ΔS (J / kgK) MnFeP 0.75 Ge 0.25 327 3 11.0 Mn 1.1 Fe 0.9 P 0.81 Ge 0.19 260 7 14.0 Mn 1.1 Fe 0.9 P 0.78 Ge 0.22 296 5 20.0 Mn 1.1 Fe 0.9 P 0.75 Ge 0.25 330 2 13.0 Mn 1.2 Fe 0.8 P 0.81 Ge 0.19 220 3 7.7 Mn 1.2 Fe 0.8 P 0.75 Ge 0.25 305 3 - Mn 1.2 Fe 0.8 P 0.73 Ge 0.27 313 5 - Mn 1.3 Fe 0.7 P 0.78 Ge 0.22 203 3 5.1 Mn 1.3 Fe 0.7 P 0.75 Ge 0.25 264 1 - Bulk T c (K) ΔT hys (K) -ΔS (J / kgK) MnFeP 0.75 Ge 0.25 327 3 11.0 Mn 1.16 Fe 0.84 P 0.75 Ge 0.25 330 5 22.5 Mn 1.18 Fe 0.82 P 0.75 Ge 0.25 310 3 16.1 Mn 1.20 Fe 0.80 P 0.75 Ge 0.25 302 1 12.0 Mn 1.22 Fe 0.78 P 0.75 Ge 0.25 276 4 11.7 Mn 1.26 Fe 0.74 P 0.75 Ge 0.25 270 1 8.5 Mn 1.1 Fe 0.9 P 0.81 Ge 0.19 260 6 13.8 Mn 1.1 Fe 0.9 P 0.78 Ge 0.22 296 4 20.0 Mn 1.1 Fe 0.9 P 0.77 Ge 0.23 312 2 14.6 Mn 1.1 Fe 0.9 P 0.75 Ge 0.25 329 2 13.0 bands Mn 1.20 Fe 0.80 P 0.75 Ge 0.25 288 1 20.3 Mn 1.22 Fe 0.78 P 0.75 Ge 0.25 274 2 15.3 Mn 1.24 Fe 0.76 P 0.75 Ge 0.25 254 2 16.4 Mn 1.26 Fe 0.74 P 0.75 Ge 0.25 250 4 14.4 Mn 1.30 Fe 0.70 P 0.75 Ge 0.25 230 0 9.8

Claims (7)

  1. A process for preparing metal-based materials for magnetic cooling or heat pumps, comprising the following steps:
    a) reacting chemical elements and/or alloys in a stoichiometry which corresponds to the metal-based material in the solid phase and/or liquid phase,
    b) optionally converting the reaction product from stage a) to a solid,
    c) sintering and/or heat treating the solid from stage a) or b),
    d) quenching the sintered and/or heat treated solid from stage c) at a cooling rate in the range from 200 to 1300 K/s.
  2. The process according to claim 1, wherein the reaction in stage a) is effected by heating the elements and/or alloys together in a closed vessel or in an extruder, or by solid phase reaction in a ball mill.
  3. The process according to either of claims 1 and 2, wherein the conversion to a solid in stage b) is effected by melt spinning or spray cooling.
  4. The process according to any one of claims 1 to 3, wherein, in stage c), first sintering is effected at a temperature in the range from 800 to 1400°C and then heat treatment at a temperature in the range from 500 to 750°C.
  5. The process according to any one of claims 1 to 4, wherein the metal-based material is selected from
    (1) compounds of the general formula (I)

            (AyBy-1)2+δCwDxEz     (I)

    where
    A is Mn or Co,
    B is Fe, Cr or Ni,
    C, D, E at least two of C, D, E are different, have a non-vanishing concentration and are selected from P, B, Se, Ge, Ga, Si, Sn, N, As and Sb, where at least one of C, D and E is Ge or Si,
    δ is a number in the range from -0.1 to 0.1,
    w, x, y, z are numbers in the range from 0 to 1, where w + x + z = 1;
    (2) La- and Fe-based compounds of the general formulae (II) and/or (III) and/or (IV)

            La(FexSi1-x)13Hy     (II)

    where
    x is a number from 0.7 to 0.95;
    y is a number from 0 to 3;


            La(FexAlyCoz)13 or La(FexSiyCoz)13     (III)

    where
    x is a number from 0.7 to 0.95;
    y is a number from 0.05 to 1-x;
    z is a number from 0.005 to 0.5;


            LaMnxFe2-xGe     (IV)

    where
    x is a number from 1.7 to 1.95 and
    (3) Heusler alloys of the MnTP type where T is a transition metal and P is a p-doping metal with an electron count per atom e/a in the range from 7 to 8.5.
  6. The process according to claim 5, wherein the metal-based material is selected from at least quaternary compounds of the general formula (I) which, as well as Mn, Fe, P and optionally Sb, additionally comprise Ge or Si or As or Ge and As or Si and As, or Ge, Si and As.
  7. The process according to claim 1, having the process sequence of:
    a) reacting chemical elements and/or alloys in the solid phase in a stoichiometry which corresponds to the metal-based material in a ball mill,
    b) melt spinning the material obtained from stage a),
    c) heat treating the solid material from stage b) at a temperature in the range from 430 to 1200°C for a period of 10 seconds to 5 hours,
    d) quenching the heat treated solid material from stage c) at a cooling rate of 200 to 1300 K/s.
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EP2277180A1 (en) 2011-01-26
NZ588756A (en) 2012-05-25
KR20110036700A (en) 2011-04-08
BRPI0911771A2 (en) 2015-10-06
JP5855457B2 (en) 2016-02-09
US20110061775A1 (en) 2011-03-17
KR101553091B1 (en) 2015-09-14
AU2009242216B2 (en) 2014-03-20
TWI459409B (en) 2014-11-01
WO2009133049A1 (en) 2009-11-05
CA2721621A1 (en) 2009-11-05
JP2011523676A (en) 2011-08-18
CN102017025A (en) 2011-04-13
AU2014203376A1 (en) 2014-07-10
AU2009242216C1 (en) 2014-09-04
CN102017025B (en) 2014-06-25
TW201009855A (en) 2010-03-01
AU2009242216A1 (en) 2009-11-05

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