TW201009855A - Process for preparing metal-based materials for magnetic cooling or heat pumps - Google Patents

Abstract

The process for preparing metal-based materials for magnetic cooling or heat pumps comprises 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) if appropriate 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 of at least 100 K/s.

Description

201009855 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method of manufacturing a metal-based material for magnetic cooling or heat pump, a material of this type and its use. Such materials made in accordance with the present invention are used in magnetic cooling, heat pump or air conditioning systems. [Prior Art] Materials of this type are generally known and described, for example, in W〇 2004/068512. The magnetic cooling technique is based on the Magnetic Card Effect (MCE) and can form an alternative to the known vapor cycle cooling method. In materials exhibiting a magnetic card effect, aligning the magnetic moments of random alignment by an external magnetic field causes the material to heat up. This heat can be removed from the MCE material to the surrounding atmosphere by thermal transfer. When the magnetic field is subsequently turned off or removed, the magnetic moment returns to random alignment, which causes the material to cool below ambient temperature. This effect can be used for cooling purposes; see also Nature's Vol. 415, 2002! On the 1st of the month, the 15th to the 152th. Typically, a heat transfer medium such as water is used to remove heat from the magnetic card material. A commonly used material is obtained by a method in which a starting element or a starting alloy of the material is subjected to a solid phase reaction in a ball mill, and then pressed, sintered and heat-treated in an inert atmosphere and then gradually cooled to room temperature. This method is described, for example, in J. Appl. PhyS. 99, 2006, 08Q107. It is also possible to process by means of melt spinning. This makes it possible to achieve a more uniform distribution of the elements, which produces an improved magnetic card effect; see

Metals ’Vol. 25’ 1 month, 2006, pp. 544-549. In the method described therein, the starting element is first induced to melt in a chlorine atmosphere and then sprayed onto the rotating copper drum via a nozzle in a molten state. It was then sintered at 139994.doc 8 201009855 1000 °c and gradually cooled to room temperature. Materials obtained by known methods typically exhibit high thermal hysteresis. For example, in the Fej-type compound substituted by hydrazine or hydrazine, a large thermal hysteresis value is observed over a wide range of 1 κ κ or 1 〇 κ. These materials are therefore not well suited for magnetic card cooling. SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a metal-based material for magnetic cooling, which reduces thermal hysteresis. At the same time, a larger magnetic ® effect (MCE) should be achieved. This object is achieved according to the invention by a method for the production of a metal-based material for magnetic cooling or heat pumping. The method comprises the steps of: a) bringing the chemical elements and/or alloys into a solid phase and/or a liquid phase. Corresponding to the stoichiometric reaction of the metal-based material, b) converting the reaction product from stage a) to solids, c) sintering and/or heat treating the solid from stage a) or b), d The quenched 9 and/or heat treated solids from the stage hooks are quenched at a cooling rate of at least 1 K/s. It has been found in accordance with the present invention that thermal hysteresis can be significantly reduced when such metal-based materials are not gradually cooled to ambient temperature after sintering and/or heat treatment but are quenched at a high cooling rate. This cooling rate is at least 100 K/s. The cooling rate is preferably from 100 K/s to 10000 K/s, more preferably from 200 K/s to 1300 K/s. A particularly preferred cooling rate is from 300 K/s to 1 〇〇〇 K/s. This quenching can be achieved by any suitable cooling method, such as quenching the solid by water or an aqueous liquid (for example, via cooling water or an ice/water mixture). For example, 139994.doc 201009855, the solid can fall into the ice-cold But in the water. The solid may also be quenched by a subcooling gas such as liquid nitrogen. Other methods are known to those skilled in the art. The preferred method herein is controlled and rapid cooling. Without being bound by theory, the reduced hysteresis can be attributed to the particle size of the quenched composition. It has been gradually cooled after sintering and heat treatment in the case of H in the hitherto known &> which results in the formation of a larger particle size and thus an increase in heat. The remaining steps of the ',,,' manufacture of metal-based materials are less critical, with the consequent condition that the sintered and/or heat treated solids in the final step are quenched at the cooling rate of the present invention. This method can be applied to the manufacture of any metal-based material suitable for magnetic cooling. A typical material for magnetic cooling is a multi-metal mixture which typically contains at least three metal elements and additionally contains non-metallic elements when appropriate. The expression "metal-based material fields" is mainly composed of metals or metal elements. Generally, the ratio of the materials is at least 5% by weight, preferably at least 75 weights. A, : : at least 8. % by weight. The following is a detailed description of a suitable metal-based material: in the step (4) of the method, the metal is mainly used as the electric H or the alloy is in the solid phase or the liquid phase corresponds to the Stoichiometric conversion of metal-based materials. = Good by solid phase reaction in (4) Μ or in the machine - pure two gold =::: phase-reverse, good for the solid phase reaction 'It is especially in the ball mill. 139994.doc 201009855. This reaction is generally known; see the literature cited in the introduction. Usually 'will be present in the powder of individual elements in later metal-based materials or The alloy powder of two or more of the individual elements is mixed in a powder form in a suitable weight ratio. If necessary, the mixture may be additionally ground to obtain a microcrystalline powder mixture. It is preferred to heat the powder mixture in a ball mill, which leads to further Step comminution and good mixing, and lead to solid phase reaction of the powder mixture. Alternatively, individual elements are mixed in powder form at selected stoichiometry and subsequently melted. Combined heating in a sealed container allows for the immobilization of volatile elements and control of stoichiometry In particular, in the case of phosphorus, this element will readily evaporate in an open system. The reaction is followed by sintering and/or heat treatment of solids, which can provide a number of intermediate steps. For example, in stage a) The solid obtained in the solid can be pressed before it is sintered and/or heat treated. This increases the density of the material, so that a high density magnetic card material is present in later applications. This is particularly advantageous because the magnetic field can be reduced Within the volume, this may be associated with significant cost savings. The pressing itself is known and can be carried out with or without the presence of a press aid. It is possible to use any suitable mold for this press. Sintering and/or heat treatment, which may be stage C) after pressing a shaped object having the desired three-dimensional structure, It is possible to quench the stage d). Alternatively, it is possible to feed the solids obtained from the ball mill to the melt spinning process. The melt spinning process itself is known and described, for example, in Mehls, 139994.doc 201009855 Volume 25 'In the month of 2006, pages 544 to 549, in & WO 2004/0685l2. In these processes, the composition obtained in stage a) is melted and sprayed onto a rotating cold metal reel. This spray is achieved by means of a high pressure upstream of the nozzle or a low pressure downstream of the nozzle. Typically, a rotating copper drum or drum is used, which may be additionally cooled as appropriate. The copper drum is preferably 1 pawl to buckle m/s, especially 20 The surface speed of m/s to 30 m/s is rotated. On the copper drum, the liquid composition is preferably at a rate of 102 K/s to 107 K/s, more preferably at least 1 〇 4 K/s, especially 0.5. Cool down at a rate of xl 〇 6K/s to 2xl06K/s. Also as in the reaction in stage a), melt spinning can be carried out under reduced pressure or in an inert atmosphere. Melt spinning achieves a high processing rate because subsequent sintering and heat treatment can be shortened. In particular, on an industrial scale, the manufacture of metal-based materials is therefore economically significant. Spray drying also results in high processing rates. It is especially preferred to carry out melt spinning. Alternatively, in stage b), spray cooling can be carried out in which the composition from stage a) is melted into the spray tower. The spray tower can, for example, be additionally cooled. In the spray tower, a cooling rate in the range of 1"3" to K...K/s, in particular about 104 K/s, is usually achieved. The sintering and/or heat treatment of the solids is carried out in stage c), preferably It is first sintered at a temperature in the range of 800 C to 1400 C and then heat treated at a temperature ranging from 5 Torr to 750 C. This value is especially suitable for forming objects' while lower sintering and heat treatment temperatures It can be used for powders. For example, sintering can then be carried out at a temperature in the range of 50 (TC to 80 (TC). For 139994.doc 201009855 shaped objects/solids, now burned, more preferably in 1〇〇〇 (: to 13〇0. (:, especially 1100 C to 〖3〇〇t: within the range of six r 祀 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The heat treatment is carried out, preferably in the range of 1 hour to 5G hours, more preferably 2 hours to 20::, especially 5 hours to 15 hours. The heat treatment is preferably carried out for another 10 hours. 100 hours, more preferably 1 hour to (9) hours, especially hours to 5 hours. To adjust the exact time.

In the case of using the melt spinning method, sintering can usually be omitted, and the heat treatment can be remarkably shortened, for example, to 5 minutes to 5 hours, preferably 1 minute to i J. This produces a greater time advantage than the usual values of sintering for 1 hour and heat treatment hours. The sintering/heat treatment causes partial melting of the particle boundaries, so that the material is further densified. The melting and rapid cooling in stage b) thus significantly reduces the duration of stage c). This also allows the continuous manufacture of metal-based materials. According to the invention, the following sequence of processes is particularly preferred: a) subjecting the chemical oxime and/or alloy to a solid phase reaction in a ball mill corresponding to the stoichiometry of the metal-based material, b) melt spinning stage a) The material obtained, c) is from 430 C to 1200 ° C, preferably 800. (: heats the solid from stage b) at a temperature in the range of l〇〇〇°c for a period of 10 seconds or 1 minute to 5 hours, preferably 30 minutes to 2 hours, d) at 200 K The cooling rate of /s to 13 〇 0 K/s is quenched from the shaped object heat treated by 139994.doc -9- 201009855 of stage c). The method of the present invention can be applied to any suitable metal-based material, and the metal-based material is more preferably selected from the group consisting of: (1) a compound of the formula (I) wherein: (AyBy.j)2+5CwDxEz ( I) A is Μη or Co, B is Fe, Cr or Ni, and C, D and at least two of EC, D and E are different, have a non-zero degree and are selected from P, B, Se, Ge, Ga, Si, : N, As and Sb, wherein at least one of c, D and E is Ge or Si, δ is a value in the range of -0.1 to 0.1, and w, X, y, ζ are values in the range of 0 to 1. Wherein w+x+z=l La and Fe-based compounds La(Fe:xAli_x)13Hy or La(FexSibx)nHy (II) of formula (II) and/or (III) and/or (IV) Where: X is a value from 0.7 to 0.95, y is a value from 0 to 3, preferably from 〇 to 2 - La(FexAlyCoz)13 or La(FexSiyCoz)13 (Ill) where: X is a value from 0.7 to 0.95 , y is a value from 0.05 to 1-χ, ζ is a value from 0.005 to 0.5; 139994.doc 201009855 (IV)

LaMnxFe2-xGe where: x is a value from 1.7 to 1.95, and (3) ΜηΤΡ type of Heusler alloy, where τ is a transition metal, and P is the number of electrons per atom e/a from 7 to 8.5 A p-doped metal within the range. Materials which are particularly suitable according to the invention are described, for example, in WO 2004/068512; Rare Metals, Vol. 25, 2006, pages 544 to 549; J. Appl. Phys. 99.08Q107 (2006); Nature, 415 volumes 'January 10, 2002, pp. 150-152; and Physica B 327 (2003), pp. 431-437. In the compound of the above formula (I), C, D and E are preferably the same or different and are selected from at least one of P, Ge, Si, Sn and Ga. The metal-based material of the formula (I) is preferably selected from at least a quaternary compound comprising not only Mn, Fe, p and, if appropriate, sb, but additionally Ge or Si or As or Ge and Si or Ge and As or Si and As or Ge, Si and As. Preferably, at least 90% by weight, more preferably at least 95% by weight, of component a is Μη. Preferably, at least 9% by weight, more preferably at least 95% by weight, of B. Preferably at least 90% by weight, more preferably at least 95% by weight, of c is p. Preferably to v 90 weight. /. More preferably, at least % by weight is 〇e. Preferably, at least 9% by weight, more preferably at least 95% by weight, is Si. The material preferably has the general formula MnFe (PwGexSiz). X is preferably a value in the range of 〇·3 to 〇.7, which is less than or equal to ΐχ and ζ corresponds to 1-X-W. 139994.doc 201009855 The material preferably has a crystalline hexagonal FezP structure. An example of a suitable structure is MnFeP 0.45 to. 7, Ge〇 55 to 〇 3. And MnFeP0.5i0 7. , (Si/Ge) 0.5 to. 3〇. A suitable compound is additionally Mw+xFebxPuGey, wherein X is in the range of -0.3 to 〇.5 and y is in the range of 〇·1 to 0.6. Also suitable are compounds of the formula MnHxFei-xPi.yGeyzSbz wherein X is in the range of from 至3 to 0.5, y is in the range of from 0.1 to 0.6, and z is less than y and less than 〇·2. Also suitable are compounds of the formula Mni+xFei.xPhyGey.zSizi, wherein X is in the range of 〇·3 to 〇5, y is in the range of 0.1 to 0.66, z is less than or equal to y and less than 0.6 〇. The compounds based on La and Fe of II) and/or (III) and/or (IV) are La(Fe〇.90Si0.10)13, LaCFeo.^SiiuOn, La(Fe〇.880Si〇.12〇)13 , La(Fe〇.877Si〇.123)13, LaFen.8Sii.2, La(Fe0.88Si0.12)13H0.5,

La(Fe〇.88Si〇.i2)i3Hi.〇 ' LaFen.7811.3111.! ' LaFen.57Si1.43H! 3 '

La(Fe〇.88Si〇.i2)Hi.5, LaFei12Co〇.7Sii.i, LaFen^Al] 5C〇.i, LaFen.5Alj.5C0.2, LaFen.5Al1.5C0.4, LaFen.5Al1. 5Coo.5,

La (Fe〇.94Co〇.06) 11.83AI1.17, La(Fe〇.92Co〇.08) 11.83AI1.17. Suitable manganese-containing compounds are MnFeGe, MnFeo^CoojGe, MnFe〇.8Co〇_2Ge, MnFe〇.7Co〇.3Ge, MnFe〇.6Co〇.4Ge, MnFe0.5Co0.5Ge, MnFe〇.4Co〇.6Ge, MnFe〇.3Co〇.7Ge, MnFe〇.2Co〇.8Ge, MnFe〇.i5Co〇.85Ge, JMllFc〇.iC〇〇.9Ge Λ MllCoGc ' Mn.5GC2.5Sio.5 ' Μώ.5〇62*^ Ϊ ' M1I5G6J 5SIJ 5 ' MiisGeSi!, Mri5Ge3, Mn5Ge2.9Sb〇j, Mn5Ge2.gSb〇.2, Mri5Ge2.7Sb〇.3, LaMn1.9Feo.1Ge 'LaMnj 85Fe〇.15Ge 'LaMni.8Fe〇.2Ge ' (Fe〇.9Mn〇.i) 3C '(Fe〇.8Mn〇.2)3C, (Fe〇.7Mn〇.3)3C, Mn3GaC, MnAs, (Mn,Fe)As, Mni+sAs〇.8Sb 〇.2, MnAso.75Sbo.25, Mri1.1Aso.75Sbo.25, Mn1.5Aso.75Sbo.25. 139994.doc -12- 201009855 • A Haussler alloy suitable according to the invention is, for example, Fe2MnSiG.5Ge0.5,

Ni52.9Mn22.4Ga24.7, Νΐ50.9Μη24.7〇&24.4, ΝΙ55 jMlli 8.6仏26_2,

Ni5i.6Mii24.7Ga23.8, Ni52.7Mri23.9Ga23.4, CoMnSb, CoNbojMno.gSb, CoNb〇.4Mn〇.6SB, CoNbo.6Mjio.4Sb, Ni5〇Mn35Sni5, Ni5〇Mn37Sni3, MnFePo.45Aso.55, MnFeP0.47A0.53, Mn1.1Feo.9Po.47Aso.53,

MnFePo.ssi-xSixGeo.uCxsO^, x=0.26, χ=0·30, x=0.33). w The present invention is also directed to a metal-based material for magnetic cooling, which can be obtained by the method described above. Further, the present invention relates to a metal-based material for magnetic cooling as defined above with reference to a composition not including an As-containing material, the composition having an average crystal size of 10 nm to 400 nm, more preferably It is in the range of 20 nm to 200 nm, especially 30 nm to 80 nm. The average crystal size can be determined by X-ray diffraction. When the crystal size becomes too small, the maximum magnetic card effect is lowered. Conversely, when the crystal size is too large, the hysteresis of the system increases. As described above, the metal-based material of the present invention is preferably used in magnetic cooling. In addition to containing a magnet (preferably a permanent magnet), the corresponding freezer also contains a metal-based material as described above. Cooling of computer chips and solar generators is also possible. Other areas of use are heat pump and air conditioning systems. • The metal-based material produced by the method of the present invention can be in any desired solid form. It may also be in the form of a sheet, a strip, a thread, a powder or in the form of a shaped object. Shaped objects such as monoliths or honeycombs can be produced, for example, by a hot extrusion process. For example, a cell density of 400 CPI to 1600 CPI or above 1600 CPI may be present. Sheets obtainable by the 139994.doc -13 - 201009855 roll method are also preferred in accordance with the present invention. Advantageous non-porous shaped objects are those formed from thin shaped materials, such as tubes, plates, meshes, grids or rods 1 which may also be formed by metal injection molding (MIM) methods in accordance with the invention. The invention is illustrated in detail by the following examples. [Examples] Example Example 1 A vacuum quartz ampoule containing a pressed sample of MnFePGe was stored at ii ° ° C for ○ hours to sinter the powder. This sintering was followed by heat treatment at 65 (rc for 60 hours to produce homogenization. The substitution was slowly cooled to room temperature in an oven, but the sample was immediately quenched to room temperature in water. Quenching in water caused some surface of the sample to be produced. Degree of oxidation. The external oxidation shell was removed by dilute acid etching. The XRD pattern showed that all samples were crystallized in a Fej-type structure. The following compositions were obtained:

MnMFeo.gPo.g^eo.^; MnMFe〇.9P〇.78Ge〇.22; Mn^jFeo.pPo 75Ge〇 25 ; and Mn^Feo.sPo ^Geo”9. For these samples in a given order, the observed values of thermal hysteresis are 7 Κ, 5 Κ, 2 Κ, and 3 Κ. This thermal hysteresis has been greatly reduced compared to slow-cooled samples with thermal hysteresis greater than 1 〇 κ. The thermal hysteresis was measured in a magnetic field of 0.5 Tessia. The MniiFeQ9BQ78GeQ22, which is close to the Curie temperature with an elevated magnetic field isothermal magnetization, is observed to produce a large MCE2 field induced transition behavior for a magnetic field of up to 5 Tesla. The Curie temperature can be adjusted by changing the Mn/Fe ratio and the Ge concentration, and the thermal hysteresis value can be adjusted as such. 139994.doc * 14 - 201009855 For the maximum magnetic field change from 0 to 2 Tesla, the magnetic entropy change calculated from DC magnetization using the Maxwell relationship is 14 for the first three samples. J/kgK, 20 J/kgK and 12.7 J/kgK. Curie and thermal hysteresis decrease as the Mn/Fe ratio increases. Therefore, the MnFePGe compound exhibits a relatively large MCE value in a low magnetic field. The thermal hysteresis of these materials is extremely low. Example 2

Melt spinning of MnFeP (GeSb) is first produced in a ball mill with high energy input and by solid phase reaction as described in WO 2004/068512 and J. Appl. Phys. 99, 08 Q107 (2006) MnFeP (Ge, Sb) alloy. The piece of material is then introduced into a quartz tube with a nozzle. The chamber was evacuated to a vacuum of 1 (2 mbar) and then filled with high purity argon. The sample was melted by means of high frequency and sprayed through a nozzle into the chamber containing the rotating copper drum due to the pressure difference. The surface speed of the wheel was adjustable and reached a cooling rate of about 105 K/s. Subsequently, the ribbon was heat treated at 900 ° C for 1 hour. X-ray diffraction measurement revealed that all samples were hexagonal Fe2P structure. Type crystallization. The smaller contaminant phase of MnO was not observed compared to the sample not produced by the melt spinning method. The values of Curie temperature, hysteresis and entropy were determined for different circumferential velocities in the melt spinning. Listed in Tables 1 and 2 below. In each case, low hysteresis temperatures were measured. 139994.doc 15· 201009855

Band V(m/s) Tc(K) ΔΤ潷 (K) -AS(J/kgK) Mnl.2Fe0.gp0.73Ge0.25sb0.02 30 269 4 12.1 Mni.2Fe〇.8P〇.7〇 Ge〇.2〇Sb〇.i〇30 304 4.5 19.0 45 314 3 11.0 MnFeP〇.7〇Ge〇.2〇Sb〇.i〇20 306 8 17.2 30 340 3 9.5 MnFePo.75Geo.25 20 316 9 13.5 40 302 8 - Mni"Fe〇.9P〇.78Ge〇.22 20 302 5 - 40 299 7 MnuFeo.9Po.75Geo.25 30 283 9 11.2 Mn1.2FeogP0.75GGo.25 30 240 8 14.2 MnnFeo.9Po.73Geo .27 30 262 5 10.1 Block Tc(K) ΔΤ hysteresis (K) -AS(J/kgK) MnFeP〇.75Ge〇25 327 3 11.0 Mn1.1Feo.9Po.8iGeo.19 260 7 14.0 MnuFeo.9Po.7sGeo .22 296 5 20.0 MnnFeo.9Po.75Geo.25 330 2 13.0 Mni.2Fe〇.8P〇.8iGe〇.i9 220 3 7.7 Mni .2F eo.gPo.75Geo.25 305 3 - Mn1.2Feo.gPo.73Geo .27 313 5 - Mni .3F e〇. 7P0.7sGe〇22 203 3 5.1 Mn1.3Fe0.7P0.75Ge0.25 264 1 - Table 2 Block Tc(K) ΔΤ» After (K) -AS(J/ kgK) MnFeP〇.75Ge〇.25 327 3 11.0 Mn1.i6Feo.84Po.75Geo.25 330 5 22.5 Mni. 18Fe0.82P0.75Ge0.25 310 3 16.1 Mni.2〇Fe〇.8〇P〇.75Ge〇 .25 302 1 12.0 Mni .22Fe0.78P0.75Ge0. 25 276 4 11.7 Mn1.20Fe0.74P0.75Ge0.25 270 1 8.5 Mn1.1Feo.9Po.8iGeo.19 260 6 13.8 Mni. 1Feo.9Po.78Geo.22 296 4 20.0 MnuFeo.9Po.77Geo.23 312 2 14.6 MnuFeo.9Po.75Geo.25 329 2 13.0 strips Mni .2〇Fe〇.8〇P〇.75Ge〇.25 288 1 20.3 Μη] .22Feo.78Po.75Geo.25 274 2 15.3 Mn1.24Feo.7ePo. 75Geo.25 254 2 16.4 Mni .26Feo.74Po.75Geo.25 250 4 14.4 Mni.3〇Fe〇,7〇P〇.75Ge〇.25 230 0 9.8 139994.doc •16-

Claims (1)

201009855 VII. Patent application scope: ι A method for manufacturing a metal-based material for magnetic cooling or heat pumping, which comprises the following steps: a) Corresponding to a chemical element and/or alloy in a solid phase and/or a liquid phase a stoichiometric reaction of the metal-based material, b) converting the reaction product from stage a) to a solid, c) sintering and/or heat-treating the solid from the stage hook or ..., at least 1 The cooling rate of 〇〇κ/s is quenched from the burnt enthalpy and/or heat treated solid of stage c). 2. The method of claim i, wherein the quenching in the stage is performed at a cooling rate in the range of 2 〇〇 k/s to 1300 K/s. 3. The method of claim 1, wherein the reaction in stage a) is carried out by heating the elements and/or alloys together in a sealed container or in an extruder or in a ball mill. Come on. The method of any one of claims 1 to 3, wherein the conversion to solids in stage b) is carried out by melt spinning or spray cooling. 5. The method of any one of claims 1 to 3, wherein in the step of homogenizing, the sintering is first carried out at a temperature in the range of 800 T: to 1400 t and the subsequent heat treatment is at 500. 6. The method of any one of claims 1 to 3, wherein the metal-based material is selected from the group consisting of: (1) a compound of the formula (I) AyBy.i)2+5CwDxEz (I) where: 139994.doc 201009855 ABC, D and E are Mn or Co, which are Fe, Cr or Ni, at least two of c, D and E, having a non-zero concentration and Is selected from the group consisting of P, B, Se, Ge, Ga, Si, Sn, N, As, and Sb, wherein at least one of C, D, and E is Ge or Si, and is a value in the range of -0.1 to 0.1. , w, x, y, z are the values in the range, where w+x+z=1; (2) the formula (II) and/or (III) and/or (1乂) are based on Compound LaCFexAUsHj^LaiFexSij.xLHy (π) where: X is a value of 〇·7 to 0.95, y is a value of 0 to 3; La(FexAlyCoz)134La(FexSiyCoz)13 where: a value of 0.7 to 0.95, 〇 〇5 to 1-x, a value of 0.005 to 0.5; LaMnxFe2.xGe (IV) δ X y Z where x (III) is a value of 1.7 to 1.95, and (3) ΜηΤΡ type Hausler alloy , where τ is the transition metal and p is the electron number e/a of each) A p-doped metal in the range of 7 to 8.5. The method of claim 6, wherein the metal-based material is selected from the group consisting of: 139994.doc 201009855 • at least a quaternary compound of the formula (I), which is not only Containing Μη, Fe, P and, if appropriate, Sb, and additionally including Ge or Si or As or Ge and As or Si and As, or Ge, Si and As 〇8. Metal for magnetic cooling or heat pumping A material of the type which can be obtained by the method of any one of claims 1 to 3. 9. A metal-based material for magnetic cooling or heat pump, which can be obtained by the method of claim 6 Obtained 'excluding containing materials and an average crystal size in the range of 10 nm to 400 nm. · 1〇_The metal-based material of claim 8 is used in magnetic cooling heat pumps or air conditioning systems. 139994.doc 201009855 IV. Designation of the representative representative: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: (none) 139994.doc